Charge control resin and manufacturing method of the same

ABSTRACT

Here is provided a charge control resin which is prompt in charge rising up, excellent in electrostatic charging propensity and easy in manufacturing. This charge control resin contains a polymer as an active ingredient having a constituent unit represented by following Formula (1) 
                         
in the Formula (1), R 1  is independent of one another, and is a hydrogen atom, a hydroxyl group, a halogen atom, a carboxy-containing group, a straight-chained or branched alkyl group having 1-18 carbon atoms, or a straight-chained or branched alkoxy group having 1-18 carbon atoms; R 2  is a hydrogen atom, a hydroxyl group, a halogen atom, a carboxy-containing group, a straight-chained or branched alkyl group having 1-18 carbon atoms, or a straight-chained or branched alkoxy group having 1-18 carbon atoms; g is a number of 1-3; h is a number of 1-3; and M is a hydrogen atom, an alkali metal, a straight-chained or branched alkyl group having 1-18 carbon atoms, an ammonium radical or a mixture of any of these.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. patent applicationSer. No. 14/115,450, now U.S. Pat. No. 8,883,946, which was filed onNov. 4, 2013, and which is a 35 U.S.C. §371 national stage patentapplication of international patent application PCT/JP2012/062685, filedon May 17, 2012, which claims priority to Japanese patent application JP2011-111796, filed on May 18, 2011.

TECHNICAL FIELD

The present invention relates to a charge control resin which is used tocontrol an electric charge of a toner for electrophotography and that ofa powdery paint for electrostatic powder coating, and which contains apolymer as its active ingredient having a constituent unit that isobtained from a particular styrene derivative or a monomer thereof.

BACKGROUND ART

Conventionally, a styrene-based resin has been widely used in householdelectric appliances, business machines, household utensils, foodcontainers, packaging materials, toys and others for the reason that itis well balanced in price, transparency, mechanical strength, andformability. Also, it is possible to make a styrene-based resin throughdiverse methods and in general, and it is molded by means of injectionmolding, extrusion molding, blow molding, vacuum molding, or injectionmolding etc. The styrene-based resin is mainly produced by thermalpolymerization or radical polymerization method, which latter makes useof an initiator. Typical manufacturing processes of it are bulkpolymerization method and suspension polymerization method, and theformer is more popular for the reasons of smaller product contaminationwith impurities such as dispersant, and lower cost with advantage.

A styrene monomer which becomes a raw material for a styrene-based resinis used as a starting material for various synthetic resins as well, andas such is an industrially important monomer. For example, in the fieldof electrophotography, it is used as a binding resin for toner, forexample: polystyrene; poly-p-chlorostyrene; polyvinyl toluene;styrene-p-chlorostyrene copolymer; styrene-vinyl toluene copolymer;styrene-vinylnaphthalene copolymer; styrene-acrylic acid estercopolymer; styrene-methacrylic acid ester copolymer;styrene-α-chloromethacrylic acid methyl copolymer; styrene-acrylonitrilecopolymer; styrene-vinylmethylether copolymer; styrene-vinylethylethercopolymer; styrene-vinylmethyl ketone copolymer; styrene-butadienecopolymer; styrene-isoprene copolymer; styrene-acrylonitrile-indenecopolymer; and a styrene-based copolymer which is made through areaction between a styrene monomer and a comonomer selected fromacrylamide, vinyl chloride, vinyl acetate, vinyl benzonate, ethylene,propylene, butylene, vinyl methyl ether, and vinyl isobutyl ether.

A toner for electrophotography is pre-added with a charge control agentfor the purposes of increasing a rising speed of charging of the toner,improving the charging characteristics through sufficient charging ofthe toner and thereby properly controlling and stabilizing a electriccharge amount, and increasing the rate of development of theelectrostatic latent charge to thereby forming a clear image. Examplesof the currently known charge control agent in the field of thetechnology in issue include, as negatively chargeable charge controlagents, a metallic complex salt of mono azo dye, a metallic complex saltof hydroxyl carboxylic acid or dicarboxylic acid or an aromatic diol,and a resin containing an acidic component. Examples of the currentlyknown positively chargeable charge control agents include nigrosinedyes, azine dyes, triphenylmethane-based dyes, quarternary ammoniumsalt, and polymers having quarternary ammonium salt on a side chainthereof. With respect to the above-named charge control agents, there isa room for improvement against the problems such as a difficulty inbalancing between the image density and fogging, a difficulty inattaining a sufficient image density under a high humidity condition, apoor dispersion in the resin, and harmful effects imparted to thepreservation stability, the fixity, and the anti-offset characteristic.

As a trial for attaining such improvements, there have been efforts madeto improve the compatibility to the toner resin and to use a resinhaving charge control property as the toner for electrostatic chargeimage developing. For example, in Patent Document 1 there is described atoner for electrostatic charge image developing, which contains as thecharge control agent a condensate of a salicylic acid having asubstituent. Also, Patent Document 2 describes a toner for electrostaticcharge image developing, which contains at least a salicylic acid resin.In addition, in Patent Document 3 there is described a toner forelectrostatic charge image developing which contains a copolymerconsisting at least of a styrene derivative and a styrene derivativehaving a carboxyl group and a hydroxyl group. Furthermore, PatentDocument 4 describes a negatively chargeable toner containing anegatively chargeable charge control agent which consists of a polymerfrom a polymerizable composition containing a radical polymerizablemonomer having a diphenyl group which may be substituted with a carboxylgroup. Also, Patent Document 5 describes a negatively chargeable tonerfor electrophotography containing a charge control agent in an amount of0.1 through 10 weight parts against 100 weight parts of a binder,wherein the charge control agent, represented by a particular chemicalformula, consists of 1 through 30 weight % of sulfoalkyl(meth)acrylicacid monomers and 99 through 70 weight % of other vinyl type monomerswhich are capable of forming a copolymer with the former. Then, PatentDocument 6 describes a toner for electrostatic image developmentcontaining a charge control agent which is a copolymer having a sulfonicacid group and which is obtained through a copolymerization among avinyl aromatic carbon hydride and a (meth)acrylate and a sulfonic acidgroup-containing (meth)acrylamide, in which the copolymerization rate ofthe sulfonic acid group-containing (meth)acrylamide is 0.1-1.8 weight %and a weight average molecular weight of the copolymer is 2,000-15,000.

In recent years, there have been made improvements in performances ofcopiers and printers so that a higher resolution in the images providedby the copiers and printers are attained among other things, and alsothere has been an expansion of system such as electrophotography systemincluding ones for low speed developing as well as those for high speeddeveloping. It has been also desired to develop such a charge controlagent that is designed to enable a better control of the charge risen upof the toner, to exhibit more excellent charging characteristics, toenable a formation of a clear and high resolution image, and to bemanufactured with simplicity. Also, a good charge control agent has beendemanded which can be used as a powdery paint, which is employed inelectrostatic powder coating wherein an electrostatically chargedpowdery paint is adsorbed to the surface of a structure by the electriccharge thereof and is burnt thereon.

PRIOR ART DOCUMENTS Patent Documents

-   Patent Document 1: Japanese Patent Application Publication    H02-190869-   Patent Document 2: Japanese Patent Application Publication    H03-105355-   Patent Document 3: Japanese Patent Application Publication    H04-016858-   Patent Document 4: Japanese Patent Application Publication    2000-298379-   Patent Document 5: Japanese Patent Application Publication    H08-179564-   Patent Document 6: Japanese Patent Application Publication    H11-184165

SUMMARY OF THE INVENTION Problems to be Solved by the Invention

The present invent was contrived in view of solving the above-mentionedproblems, and it is a purpose of the present invention to provide acharge control resin which has a high compatibility with a toner resin,is high in the speed of being charged, exhibits excellent chargingcharacteristics, and can be manufactured with simplicity.

Means to Solve the Problems

The charge control resin of the present invention, which is made inorder to attain the above-mentioned object, is characterized bycomprising a polymer as its active ingredient having a constituent unitrepresented by the following Formula (1):

in the Formula (1), R¹ is independent of one another, and is a hydrogenatom, a hydroxyl group, a halogen atom, a carboxy-containing group, astraight-chained or branched alkyl group having 1-18 carbon atoms, or astraight-chained or branched alkoxy group having 1-18 carbon atoms; R²is a hydrogen atom, a hydroxyl group, a halogen atom, acarboxy-containing group, a straight-chained or branched alkyl grouphaving 1-18 carbon atoms, or a straight-chained or branched alkoxy grouphaving 1-18 carbon atoms; g is a number of 1-3; h is a number of 1-3;and M is a hydrogen atom, an alkali metal, a straight-chained orbranched alkyl group having 1-18 carbon atoms, an ammonium radical or amixture of any of these.

It is preferable that in the Formula (1) representing the constituentunit, R¹ is the hydrogen atom, the halogen atom, or the straight-chainedor branched alkyl group having 1-18 carbon atoms.

It is preferable that in the Formula (1) representing the constituentunit, R² is the hydrogen atom.

It is preferable that in the Formula (1) representing the constituentunit, the hydroxyl group takes an ortho position of the —COOM group.

It is preferable that in the Formula (1) of the constituent unit M isthe hydrogen atom.

It is preferable that the charge control resin contains a copolymerwherein the polymer has a constituent unit represented by the Formula(1) and a constituent unit obtained from a vinyl group-containingmonomer.

Examples of the vinyl group-containing monomer, which is a monomercapable of copolymerizing with styrene derivative (ex. a styrenemonomer), include a substituted or non-substituted aromatic vinylmonomer such as styrene, α-methylstyrene, p-methylstyrene, andacrylonitrile, methacrylonitrile, acrylic acid, methyl acrylate,methacrylic acid, methyl methacrylate, and a vinyl monomer such as vinylacrylate, and also maleic anhydride and maleimide.

It is preferable that the constituent unit obtained from the vinylgroup-containing monomer is one as represented by the following Formula(2):

in the Formula (2), R³, R⁴ and R⁵ are independent of one another, andare a hydrogen atom, an alkyl group, a halogen atom, or an alkoxy group.

It is preferable that the vinyl group-containing monomer is styrene.

It is preferable that the charge control resin is such that the polymeris a product of a copolymerization reaction by which a styrenederivative represented by the following Formula (3) reacts with theafore-mentioned vinyl group-containing monomer in the presence of acopolymerization initiator:

in the Formula (3), R¹ is independent of one another, and is a hydrogenatom, a hydroxyl group, a halogen atom, a carboxy-containing group, astraight-chained or branched alkyl group having 1-18 carbon atoms, or astraight-chained or branched alkoxy group having 1-18 carbon atoms, R²is a hydrogen atom, a hydroxyl group, a halogen atom, acarboxy-containing group, a straight-chained or branched alkyl grouphaving 1-18 carbon atoms, or a straight-chained or branched alkoxy grouphaving 1-18 carbon atoms, g is a number of 1-3, h is a number of 1-3, Mis a hydrogen atom, an alkali metal, a straight-chained or branchedalkyl group having 1-18 carbon atoms, an ammonium radical or a mixtureof any of these.

The afore-mentioned charge control resin is preferably such that theafore-mentioned polymer is a copolymer which contains the constituentunit represented by the Formula (1) in an amount of 0.01 to 20 mol %.

The charge control resin is preferably such that the afore-said polymerhas a glass transition temperature of 70° C. through 150° C.

The charge control resin is preferably of a kind such that theafore-mentioned polymer shows weight decrease in a measurement of itsweight at temperatures from 300° C. to 400° C. by a differential thermalthermogravimetric analysis.

The charge control resin is preferably of a kind such that theafore-mentioned polymer has a number average molecular weight (Mn) of5000-30000 and a weight average molecular weight (Mw) of 4000-300000 asmeasured by gel permeation chromatography respectively, and morepreferably the molecular weight distribution (Mw/Mn) is controlled to be1-15.

It is preferable that the charge control resin is such that theafore-mentioned polymer has a volume resistive value of0.1×10¹⁶−7.0×10¹⁷ Ωcm.

The charge control agent of the present invention is characteristic inthat it contains as an active ingredient a styrene derivativerepresented by the following Formula (3) or contains as an activeingredient a charge control resin which is a polymerization product ofthe styrene derivative:

in the Formula (3), R¹ is independent of one another, and is a hydrogenatom, a hydroxyl group, a halogen atom, a carboxy-containing group, astraight-chained or branched alkyl group having 1-18 carbon atoms, or astraight-chained or branched alkoxy group having 1-18 carbon atoms; R²is a hydrogen atom, a hydroxyl group, a halogen atom, acarboxy-containing group, a straight-chained or branched alkyl grouphaving 1-18 carbon atoms, or a straight-chained or branched alkoxy grouphaving 1-18 carbon atoms; g is a number of 1-3; h is a number of 1-3;and M is a hydrogen atom, an alkali metal, a straight-chained orbranched alkyl group having 1-18 carbon atoms, an ammonium radical or amixture of any of these.

A method of using the charge control resin of the present invention ischaracteristic in that the charge control resin containing as an activeingredient a polymer having a constituent unit represented by thefollowing Formula (1) is used for controlling the charge:

in the Formula (1), R¹ is independent of one another, and is a hydrogenatom, a hydroxyl group, a halogen atom, a carboxy-containing group, astraight-chained or branched alkyl group having 1-18 carbon atoms, or astraight-chained or branched alkoxy group having 1-18 carbon atoms; R²is a hydrogen atom, a hydroxyl group, a halogen atom, acarboxy-containing group, a straight-chained or branched alkyl grouphaving 1-18 carbon atoms, or a straight-chained or branched alkoxy grouphaving 1-18 carbon atoms; g is a number of 1-3; h is a number of 1-3;and M is a hydrogen atom, an alkali metal, a straight-chained orbranched alkyl group having 1-18 carbon atoms, an ammonium radical or amixture of any of these.

It is preferable that the method of using the charge control resin issuch that the afore-mentioned polymer has a constituent unit representedby the Formula (1) and a constituent unit represented by the followingFormula (2), which is obtained from a vinyl group-containing monomer:

in the Formula (2), R³, R⁴ and R⁵ are independent of one another, andare a hydrogen atom, an alkyl group, a halogen atom, or an alkoxy group.

A method for manufacturing the charge control resin of the presentinvention is characteristic in that, the method comprises a step forobtaining a polymer in a reaction system involving as a monomer at leasta styrene derivative represented by the following Formula (3), themonomer is polymerized to thereby obtain a charge control resin whichcontains the thus obtained polymer as an active ingredient:

in the Formula (3), R¹ is independent of one another, and is a hydrogenatom, a hydroxyl group, a halogen atom, a carboxy-containing group, astraight-chained or branched alkyl group having 1-18 carbon atoms, or astraight-chained or branched alkoxy group having 1-18 carbon atoms; R²is a hydrogen atom, a hydroxyl group, a halogen atom, acarboxy-containing group, a straight-chained or branched alkyl grouphaving 1-18 carbon atoms, or a straight-chained or branched alkoxy grouphaving 1-18 carbon atoms; g is a number of 1-3; h is a number of 1-3;and M is a hydrogen atom, an alkali metal, a straight-chained orbranched alkyl group having 1-18 carbon atoms, an ammonium radical or amixture of any of these.

In the method for manufacturing the charge control resin, the monomerpreferably involves a vinyl group-containing monomer represented by thefollowing Formula (4):

in the Formula (4), R³, R⁴ and R⁵ are independent of one another, andare a hydrogen atom, a straight-chained or branched alkyl group having1-8 carbon atoms, a straight-chained or branched alkoxy group having 1-8carbon atoms, or a halogen atom.

Effects of the Invention

The charge control resin of the present invention is excellent in chargecontrollability, and significantly prompt in charge rise-up, and can becharged negatively and can retain the electric charge amount uniformlyand stably at high level for a long time. For this reason it is possibleto dependably obtain an output image which is clear and of a highresolution. This charge control resin can be used effectively fordiverse toners including ones for low speed copying and ones for highspeed copying. Also, this charge control resin can be employed as thepowdery paint for use in electrostatic powder coating.

The polymer to constitute the active ingredient of this charge controlresin has a constituent unit represented by the Formula (1), which has acharge control function and a polymerization function, and theconstituent unit has a repetitive unit obtained from styrenederivatives. Or else it has the repetitive units consisting of theconstituent units of the identical structure as a result of a reactionafter a polymerization and a synthesis of a polymer. This polymer canhave a constituent unit obtained from a vinyl group-containing monomerin addition to the afore-mentioned repetitive unit. A copolymer havingthe constituent unit represented by the Formula (1) and a constituentunit obtained from a vinyl group-containing monomer can be used as aneffective ingredient of a charge control resin on account of its chargeimparting property and charge controllability linked to the fact thatthey co-own the phenyl skeleton (benzene ring skeleton) and the —COOMgroup in the repetitive unit, especially the phenyl group, the carboxylgroup (—COOM) and the hydroxyl group (—OH), and thus the polymer isusable as a charge control resin. Also, the styrene derivative toconstitute the repetitive unit of the polymer can be used as the chargecontrol monomer which constitutes the polymer of the charge controlresin (styrene-based resin) containing the carboxyl group and thehydroxyl group. Furthermore, it can be used independently as a chargecontrol agent.

The charge control agent of the present invention is high incompatibility toward a toner resin, can be uniformly dispersed, canexhibit a sufficiently high chargeability, and also is excellent infastness and thus can retain the chargeability sustainably.

According to the method of manufacturing the charge control resin of thepresent invention, it is possible to make conveniently a styrene-basedresin having a good charge controlling function.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a drawing showing a chart of nuclear magnetic resonancespectrum of a styrene derivative of Example A1, used for the chargecontrol resin to which the present invention is applied.

FIG. 2 is a drawing showing a chart of nuclear Overhauser effect linkedto the nuclear magnetic resonance spectrum of a styrene derivative ofExample A1, used for the charge control resin to which the presentinvention is applied.

FIG. 3 is a drawing showing a chart of infrared absorption spectrum ofthe styrene derivative of Example A1, used for the charge control resinto which the present invention is applied.

FIG. 4 is a drawing showing a chart of a result of differentialthermal/thermogravimetric analysis on the styrene derivative of ExampleA1, used for the charge control resin to which the present invention isapplied.

FIG. 5 is a drawing showing a chart of a result of liquidchromatography/mass spectrometry analysis on the styrene derivative ofExample A1, used for the charge control resin to which the presentinvention is applied.

FIG. 6 is a drawing showing a chart of nuclear magnetic resonancespectrum of a styrene derivative of Example A2, used for the chargecontrol resin to which the present invention is applied.

FIG. 7 is a drawing showing a chart of a result of differentialthermal/thermogravimetric analysis on the styrene derivative of ExampleA2, used for the charge control resin to which the present invention isapplied.

FIG. 8 is a drawing showing a chart of a result of differentialthermal/thermogravimetric analysis on a styrene derivative of ExampleA5, used for the charge control resin to which the present invention isapplied.

FIG. 9 is a drawing showing a chart of infrared absorption spectrum of astyrene derivative of Example A14, used for the charge control resin towhich the present invention is applied.

FIG. 10 is a drawing showing a chart of a result of differentialthermal/thermogravimetric analysis on the styrene derivative of ExampleA14, used for the charge control resin to which the present invention isapplied.

FIG. 11 is a drawing showing a chart of nuclear magnetic resonancespectrum of a copolymer of Example B1, used as the charge control resinto which the present invention is applied.

FIG. 12 is a drawing showing a chart of infrared absorption spectrum ofa copolymer of Example B1, used as the charge control resin to which thepresent invention is applied.

FIG. 13 is a drawing showing a chart of a result of differentialthermal/thermogravimetric analysis on a copolymer of Example B1, used asthe charge control resin to which the present invention is applied.

FIG. 14 is a drawing showing a chart of molecular weight distribution ofthe copolymer of Example B1, used as the charge control resin to whichthe present invention is applied.

FIG. 15 is a drawing showing a chart of glass transition temperatures ofthe copolymer of Example B1, used as the charge control resin to whichthe present invention is applied.

FIG. 16 is a drawing showing a chart of a result of differentialthermal/thermogravimetric analysis on a copolymer of Example B2, used asthe charge control resin to which the present invention is applied.

FIG. 17 is a drawing showing a chart of molecular weight distribution ofthe copolymer of Example B2, used as the charge control resin to whichthe present invention is applied.

FIG. 18 is a drawing showing a chart of a result of differentialthermal/thermogravimetric analysis on a copolymer of Example B3, used asthe charge control resin to which the present invention is applied.

FIG. 19 is a drawing showing a chart of molecular weight distribution ofthe copolymer of Example B3, used as the charge control resin to whichthe present invention is applied.

FIG. 20 is a drawing showing a chart of a result of differentialthermal/thermogravimetric analysis on a copolymer of Example B12, usedas the charge control resin to which the present invention is applied.

FIG. 21 is a drawing showing a chart of a result of differentialthermal/thermogravimetric analysis on a copolymer of Example B13, usedas the charge control resin to which the present invention is applied.

FIG. 22 is a drawing showing a chart of a result of differentialthermal/thermogravimetric analysis on a copolymer of Example B18, usedas the charge control resin to which the present invention is applied.

FIG. 23 is a drawing showing a chart of a result of differentialthermal/thermogravimetric analysis on a copolymer of Example B23, usedas the charge control resin to which the present invention is applied.

FIG. 24 is a drawing showing electric charge amounts as the result of anelectrostatic propensity test A on charge control agents to which thepresent invention is applied and on ones to which the present inventionis not applied.

FIG. 25 is a drawing showing electric charge amounts as the result of anelectrostatic propensity test B on charge control agents to which thepresent invention is applied and on ones to which the present inventionis not applied.

FIG. 26 is a drawing showing electric charge amounts as the result of anelectrostatic propensity test A on charge control resins to which thepresent invention is applied and on ones to which the present inventionis not applied.

FIG. 27 is a drawing showing electric charge amounts as the result of anelectrostatic propensity test A on charge control resins to which thepresent invention is applied and on ones to which the present inventionis not applied.

FIG. 28 is a drawing showing electric charge amounts as the result of anelectrostatic propensity test A on charge control resins to which thepresent invention is applied and on ones to which the present inventionis not applied.

FIG. 29 is a drawing showing electric charge amounts as the result of anelectrostatic propensity test B on charge control resins to which thepresent invention is applied and on ones to which the present inventionis not applied.

FIG. 30 is a drawing showing electric charge amounts as the result of anelectrostatic propensity test B on charge control resins to which thepresent invention is applied and on ones to which the present inventionis not applied.

FIG. 31 is a drawing showing electric charge amounts as the result of anelectrostatic propensity test B on charge control resins to which thepresent invention is applied and on ones to which the present inventionis not applied.

MODE FOR CARRYING OUT THE INVENTION

Hereunder, the examples, wherein the present invention is embodied, willbe explained in detail. However it shall not be understood that thescope of the present invention is limited by the examples.

The charge control resin of the present invention contains as an activeingredient: a polymer having a repetition of a constituent unitrepresented by the afore-given Formula (1), which is obtained from astyrene derivative represented by the Formula (3) and used as a monomer;or a polymer having a repetition of a constituent unit represented bythe identical Formula (1), this constituent unit of the identicalstructure being obtained as a result of a reaction after apolymerization and a synthesis of the polymer. The constituent unitrepresented by the Formula (1) and the styrene derivative to constitutethe constituent unit co-own a phenyl skeleton (i.e., styrene structure)having a vinyl group in the same molecule and a phenyl skeleton (i.e., askeleton structure of aromatic oxycarbonic acid) having a —COOM groupand a hydroxyl group in the same molecule. Further, the repeated unitrepresented by the Formula (1) and the styrene derivative are of astructure wherein the phenyl skeletons are connected with each otherthrough —CH₂—O—, —CH₂CH₂—O—, or —CH₂CH₂CH₂—O—.

This Styrene derivative's phenyl skeleton (benzene ring skeleton) havingthe vinyl group is an important skeleton to perform the polymerizationfunction of the styrene derivative. Further, the combination of thephenyl group having a —COOM group and a hydroxyl group with —CH₂—O—,—CH₂CH₂—O—, or —CH₂CH₂CH₂—O— makes an important skeleton responsible tothe exertion of charge imparting function. Then, the phenyl skeletonhaving a —COOM group and a hydroxyl group is a skeleton having ahydrogen bond within a molecule and between molecules which is thoughtto contribute to electric charging and having a function of ligand. Theinterplay between the two phenyl skeletons improves the electric chargeretention characteristic. It is preferable that the —COOM group and thehydroxyl group (—OH) take an ortho position with respect to each other.

Therefore, the styrene derivative used in the present invention is usedas a monomer for a polymer, and is useful as a styrene monomer which cancontrol the charge controllability. The polymer including theconstituent unit obtained from this styrene derivative makes a chargecontrol resin which becomes an active ingredient for the charge controlagent. This charge control resin (styrene-based resin) can be ahomopolymer having the constituent unit obtained from the styrenederivative, or can be a copolymer which is a product of polymerizationbetween the styrene derivative and another monomer. The charge controlresin can contain another styrene resin besides these polymers. Theconstituent unit of this charge control resin is a constituent unitpossessed by a polymer which is made by polymerizing or copolymerizingwith the styrene derivative, and can be one obtained through apolymerization involving the styrene derivative as at least one monomerelement. When used as the charge control agent, an improveddispersibility through the resin is enjoyed on account of the structuralsimilarity to the resin, which is by virtue of the substituent effect ofthe styrene derivative.

The constituent unit possessed by the polymer which becomes the activeingredient of the charge control resin of the present invention isrepresented by the following Formula (1):

In the Formula (1), the substituent R¹ is independent of one another,and may for example be: a hydrogen atom; a hydroxyl group; a halogenatom such as F, Cl and Br; a carboxy-containing group such as COOH, analkaline metal salt like COOLi, COONa and COOK, and COONH₄ or a mixtureof any of these, a straight-chained or a branched alkyl ester grouphaving 1-8 carbon atoms like COOCH₃, COOC₂H₅, COOC₃H₇, COOC₄H₉,COOC₅H₁₁, and COOC₈H₁₇; a straight-chained or branched alkyl grouphaving 1-18 carbon atoms such as methyl group, ethyl group, n-propylgroup, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,tert-butyl group, n-pentyl group, isopentyl group, hexyl group, heptylgroup, and octyl group; or a straight-chained or branched alkoxy grouphaving 1-18 carbon atoms such as methoxy group, ethoxy group, n-propoxygroup, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxygroup, tert-butoxy group, n-pentoxy group, isopentoxy group, hexyloxygroup, heptoxy group, octyloxy group, and 2-ethylhexyloxy group.

R¹ is preferably the hydrogen atom, the halogen atom, or thestraight-chained or branched alkyl group having 1-18 carbon atoms. Amongthese hydrogen atom and straight-chained or branched alkyl group having1-18 carbon atoms are more preferable. In particular, methyl group,ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutylgroup, sec-butyl group, tert-butyl group, n-pentyl group, isopentylgroup, hexyl group, heptyl group and octyl group are noted.

In the Formula (1), the substituent R² may for example be: a hydrogenatom; a hydroxyl group; a halogen atom such as F, Cl and Br; acarboxy-containing group such as COOH, an alkaline metal salt likeCOOLi, COONa and COOK, and COONH₄ or a mixture of any of these, astraight-chained or a branched alkyl ester group having 1-8 carbon atomslike COOCH₃, COOC₂H₅, COOC₃H₇, COOC₄H₉, COOC₅H₁₁, and COOC₈H₁₇; astraight-chained or branched alkyl group having 1-18 carbon atoms suchas methyl group, ethyl group, n-propyl group, isopropyl group, n-butylgroup, isobutyl group, sec-butyl group, tert-butyl group, n-pentylgroup, isopentyl group, hexyl group, heptyl group, and octyl group; or astraight-chained or branched alkoxy group having 1-18 carbon atoms suchas methoxy group, ethoxy group, n-propoxy group, isopropoxy group,n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group,n-pentoxy group, isopentoxy group, hexyloxy group, heptoxy group,octyloxy group, and 2-ethylhexyloxy group. Of these, the hydrogen atomis more preferable.

In the Formula (1), M may for example be: a hydrogen atom; an alkalinemetal such as Li, Na and K; a straight-chained or branched alkyl grouphaving 1-18 carbon atoms such as CH₃, C₂H₅, C₃H₇, C₄H₉, C₅H₁₁, C₈H₁₇,C₁₀H₂₁, C₁₂H₂₅, and C₁₈H₃₇; an ammonium radical like NH₄ ⁺ or mono-,di-, tri- or tetra-alkyl ammonium ion having 1-12 carbon atoms or amixture of any of these. As for the alkyl group, a straight-chained orbranched alkyl group having 1-8 carbon atoms is preferable.

In the Formula (1), g is an integer 1, 2 or 3, preferably 1 or 2, andmost preferably 1. Therein, h is an integer of 1, 2 or 3, and preferably1.

Therefore, it is preferable that the constituent unit is one representedby the following Formula (5).

in this Formula (5), R¹, R², M, g, and h are defined the same as above.

It is noted that the hydroxyl group (—OH group) of the constituent unitrepresented by the Formula (1) and/or the Formula (5) includes free onesor instances wherein the hydrogen atom is substituted by an alkalinemetal such as Li, Na and K, or by an ammonium radical like NH₄ ⁺ ormono-, di-, tri- or tetra-alkyl ammonium ion having 1-12 carbon atoms ora mixture of any of these.

A polymer having a constituent unit represented by the Formula (1)and/or the Formula (5) possesses a charge control function and thusapplicable as a charge control resin. The longer the carbon chain of thealkyl group in R¹ of the constituent unit of this polymer represented byFormula (1) and/or Formula (5) is, the higher the hydrophobicity of thepolymer gets; as a result this polymer has a high saturationelectrostatic propensity and thus has a good environmental stability.Therefore, a polymer obtained from a styrene derivative wherein the R¹in the styrene derivative represented by Formula (3) and/or Formula (6),which is the charge control monomer making the constituent unit of thepolymer, is butyl group, especially tert-butyl group, will exhibit agood electrostatic propensity.

It is preferable that this polymer is a copolymer which contains theconstituent unit obtained from the styrene derivative to be a degree of0.01-20 mol %. Furthermore, in consideration of the electrostaticpropensity, it is preferable that this content is 1-15 mol %, and morepreferably 2-9.5 mol %.

It is possible that the charge control resin (styrene-based resin) ofthe present invention possesses a constituent unit obtained from a vinylgroup-containing monomer in addition to the constituent unit representedby the Formula (1) and/or the Formula (5). By virtue of possessing theconstituent unit obtained from vinyl group-containing monomer, the resincan have a function of suitably controlling the electrostaticpropensity. It is possible to use as charge control agents the copolymerhaving the constituent unit represented by the Formula (1) and/or theFormula (5) and the constituent unit obtained from vinylgroup-containing monomer as well as the charge control resin(styrene-based resin) possessing such copolymer. It is preferred thatthe constituent unit obtained from the vinyl group-containing monomer isone represented by the following Formula (2).

in this Formula (2), R³, R⁴ and R⁵ are independent of one another, andare a hydrogen atom, an alkyl group, a halogen atom, or an alkoxy group.

The charge control function is improved the more with higherdispersibility through the target resin used, as occasioned by, forexample, smaller particle size, and with higher compatibility to thereceiving resin; the greatest charge control function is attained if thedispersion through the resin is carried out at molecular level.

The method for manufacturing the charge control resin (styrene-basedresin) according to the present invention, is a method including atleast a step to produce a polymer having a constituent unit representedby the Formula (1). Further, it is possible to turn the carboxyl group,which is a constituent unit, to an alkyl ester by a known method by, forexample, reacting the styrene derivative wherein M of the —COOM group iseither a hydrogen atom or an alkaline metal with an alcohol having 1-18carbon atoms. One specific method for manufacturing the charge controlresin, wherein a polymer having a constituent unit represented by theFormula (1), is a copolymer (Method A) is a method which includes a stepto synthesize a styrene derivative by reacting vinylphenyl alkylenehalide with dihydroxy aromatic carboxylic acid and a step forcopolymerizing the thus obtained styrene derivative with other monomers.Another method (Method B) includes a step to copolymerize vinylphenylalkylene halide with other monomers and a step to react the thusobtained copolymer with dihydroxy aromatic carboxylic acid or dihydroxyaromatic carboxylic acid alkyl ester.

In the present application, Method A as the chief examples will beexplained. However it is possible in Method B as well to conduct thecopolymerization step and the step to react the alkylene halide with thedihydroxy aromatic carboxylic acid while suitably controlling thereaction in response to the chemical properties.

Method A, which is one of the methods for manufacturing the chargecontrol resin (styrene-based resin) of the present invention, is amethod which includes a step to obtain a polymer by polymerizing amonomer which constitutes the constituent unit represented by theFormula (1) in a reaction system which has at least the styrenederivative as the monomer. It is, however, possible to conduct thealkyl-esterification after the synthesis of the polymer. In other words,it is possible to include a step to alkyl-esterify the —COOM group inthe constituent unit represented by the Formula (1) and/or (5) by meansof a known method such as reacting with an alcohol having 1-18 carbonatoms. A preferable method is such that the charge control monomer whichis the styrene derivative constituting the constituent unit representedby the Formula (1) is mixed with a polymerization initiator and themonomer is polymerized.

A styrene derivative to be used as the monomer is represented by thefollowing Formula (3).

The substituent R¹ in Formula (3) is independent of one another, and isfor example a hydrogen atom; a hydroxyl group; a halogen atom such as F,Cl and Br; a carboxy-containing group such as COOH, an alkaline metalsalt like COOLi, COONa and COOK, and COONH₄ or a mixture of any ofthese, a straight-chained or a branched alkyl ester group having 1-8carbon atoms like COOCH₃, COOC₂H₅, COOC₃H₇, COOC₄H₉, COOC₅H₁₁, andCOOC₈H₁₇; a straight-chained or branched alkyl group having 1-18 carbonatoms such as methyl group, ethyl group, n-propyl group, isopropylgroup, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group,n-pentyl group, isopentyl group, hexyl group, heptyl group, and octylgroup; or a straight-chained or branched alkoxy group having 1-18 carbonatoms such as methoxy group, ethoxy group, n-propoxy group, isopropoxygroup, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxygroup, n-pentoxy group, isopentoxy group, hexyloxy group, heptoxy group,octyloxy group, and 2-ethylhexyloxy group.

R¹ is preferably the hydrogen atom, the halogen atom, or thestraight-chained or branched alkyl group having 1-18 carbon atoms. Amongthese, the hydrogen atom and the straight-chained or branched alkylgroup having 1-18 carbon atoms are more preferable. In particular,methyl group, ethyl group, n-propyl group, isopropyl group, n-butylgroup, isobutyl group, sec-butyl group, tert-butyl group, n-pentylgroup, isopentyl group, hexyl group, heptyl group and octyl group arenoted.

The substituent R² may for example be: a hydrogen atom; a hydroxylgroup; a halogen atom such as F, Cl and Br; a carboxy-containing groupsuch as COOH, an alkaline metal salt like COOLi, COONa and COOK, andCOONH₄ or a mixture of any of these, a straight-chained or branchedalkyl ester group having 1-8 carbon atoms like COOCH₃, COOC₂H₅, COOC₃H₇,COOC₄H₉, COOC₅H₁₁, and COOC₈H₁₇; a straight-chained or branched alkylgroup having 1-18 carbon atoms such as methyl group, ethyl group,n-propyl group, isopropyl group, n-butyl group, isobutyl group,sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group,hexyl group, heptyl group, and octyl group; or a straight-chained orbranched alkoxy group having 1-18 carbon atoms such as methoxy group,ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group,isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group,isopentoxy group, hexyloxy group, heptoxy group, octyloxy group, and2-ethylhexyloxy group. Of these, the hydrogen atom is more preferable.

M is, for example, selected from: a hydrogen atom; an alkali metal suchas Li, Na and K; an ammonium radical exemplified by NH₄ ⁺ and mono-,di-, tri- or tetra-alkyl ammonium ion having an alkyl group with 1-12carbon atoms or a mixture of any of these, and a straight-chained orbranched alkyl group having 1-18 carbon atoms such as CH₃, C₂H₅, C₃H₇,C₄H₉, C₅H₁₁, C₈H₁₇, C₁₀H₂₁, C₁₂H₂₅, and C₁₈H₃₇. As for the alkyl group,the straight-chained or branched alkyl group having 1-8 carbon atoms ispreferable.

In Formula (3), g is exemplified as an integer 1, 2 or 3, preferably 1or 2, and most preferably 1. Therein, h is exemplified as an integer 1,2 or 3, and preferably 1.

Among others, it is preferable if, as shown in under-shown Formula (6),the hydroxyl group takes an ortho position of the —COOM group, because asynergistic effect of the —COOM group and the hydroxyl group becomesstronger, which contributes to the charging effect. By polymerizing thisstyrene derivative, the constituent unit represented by the Formula (5)is obtained.

In the Formula (6), R², g, h and M are respectively the same as above.

It is noted that the hydroxyl group (—OH group) of the constituent unitrepresented by the Formula (3) and/or the Formula (6) includes instanceswherein the hydrogen atom is substituted by an alkaline metal such asLi, Na and K, or by an ammonium radical exemplified by NH₄ ⁺ or mono-,di-, tri- or tetra-alkyl ammonium ion having 1-12 carbon atoms or amixture of any of these.

The styrene derivative represented by the Formula (3) or the Formula (6)is more specifically exemplified by the following formula. But thepresent invention is not limited thereby.

TABLE 1 (3-a)

Exam- Substi- ples tution of Position Chem- of Vinyl ical Group R² g R¹h M a1-1 4′- H 1 H 1 H a1-2 4′- H 1 5-tert-C₄H₉ 1 H a1-3 4′- H 15-iso-C₈H₁₇ 1 H a1-4 4′- H 1 5-iso-C₃H₇ 1 Na a1-5 4′- H 1 5-CH₃ 1 H a1-64′- 3′-OCH₃ 2 5-F 2 NH₄ 6-OCH₃ a1-7 4′- 3′-OH 2 5-COOH 1 H a1-8 4′-3′-Br 1 2-OC₂H₅ 1 Na a1-9 4′- 3′-CH₃ 3 6-F 1 K a1-10 4′- 3′-Cl 15-tert-OC₄H₉ 1 H, Na a1-11 4′- 3′-F 1 2-OCH₃ 1 Li a1-12 4′- 3′-tert- 12-OH 2 NH₄ C₄H₉ 5-CH₃ a1-13 4′- 3′-iso- 1 2-OCH₃ 1 H C₈H₁₇ a1-14 4′-3′-Br 1 2-tert-C₄H₉ 2 Na 5-tert-C₄H₉ a1-15 4′- 3′-iso- 3 5-Br 1 K C₃H₇a1-16 4′- H 2 5-I 1 H a1-17 4′- 3′-CH₃ 1 5-Cl 1 Li a1-18 4′- H 15-tert-C₄H₉ 1 H, Na a1-19 4′- H 1 H 1 H, Na a1-20 4′- H 1 5-iso-C₃H₇ 1 Ha1-21 4′- H 2 5-tert-C₄H₉ 1 H a1-22 4′- H 1 5-iso-C₄H₉ 1 H, Na a1-23 4′-H 1 5-CH₃ 1 NH₄ a1-24 4′- H 1 5-iso-C₈H₁₇ 1 K a1-25 4′- H 1 H 1 Na a1-264′- H 1 H 1 CH₃ a1-27 4′- H 1 H 1 C₂H₅ a1-28 4′- H 1 H 1 n-C₄H₉ a1-294′- H 1 5-tert-C₄H₉ 1 CH₃ a1-30 4′- H 1 5-iso-C₃H₇ 1 CH₃ a1-31 4′- H 15-Cl 1 n-C₈H₁₇ a1-32 4′- 3′-C₂H₅ 1 5-tert-C₄H₉ 1 CH₃ a1-33 4′- H 1 H 1(C₄H₉)₄N a1-34 4′- H 1 5-tert-C₄H₉ 1 (C₂H₅)₂NH₂

TABLE 2 Exam- ples of Substitution Chem- Position of ical Vinyl Group R²g R¹ h M a2-1 5′- H 1 H 1 H a2-2 5′- H 1 5-tert-C₄H₉ 1 H a2-3 5′- H 15-iso-C₈H₁₇ 1 H a2-4 5′- H 1 5-iso-C₃H₇ 1 H a2-5 5′- H 1 5-CH₃ 1 H a2-65′- 4′-iso-C₃H₇ 2 2-F 2 H 5-OCH₃ a2-7 5′- 4′-OCH₃ 1 5-tert-OC₄H₉ 1 NH₄a2-8 5′- 6′-OC₂H₅ 1 2-OCH₃ 1 H a2-9 5′- 2′-COOH 1 2-OH 2 H, Na 5-CH₃a2-10 5′- 4′-Cl 2 5-OCH₃ 1 K a2-11 5′- 2′-OCH₃ 1 2-iso-C₃H₇ 2 Na5-iso-C₃H₇ a2-12 5′- 2′-OCH₃ 3 5-Br 1 Li a2-13 5′- 3′-OH 1 5-I 1 NH₄a2-14 5′- 6′-Br 1 5-Cl 1 H a2-15 5′- H 2 H 1 H a2-16 5′- H 2 5-tert-C₄H₉1 H a2-17 5′- H 1 5-tert-C₄H₉ 1 H, Na a2-18 5′- H 1 5-CH₃ 1 NH₄ a2-195′- H 1 5-iso-C₈H₁₇ 1 K a2-20 5′- H 1 H 1 CH₃ a2-21 5′- H 1 H 1 C₂H₅a2-22 5′- H 1 H 1 n-C₄H₉ a2-23 5′- H 1 5-tert-C₄H₉ 1 CH₃ a2-24 5′-4′-C₂H₅ 1 H 1 C₂H₅ a2-25 5′- H 1 H 1 (C₃H₇)₄N

TABLE 3 Exam- ples of Substitution Chem- Position of ical Vinyl Group R²g R¹ h M a3-1 6′- H 1 H 1 H a3-2 6′- H 1 5-tert-C₄H₉ 1 H a3-3 6′- H 15-iso-C₈H₁₇ 1 H, Na a3-4 6′- H 1 5-iso-C₃H₇ 1 Na a3-5 6′- 3′-OCH₃ 26-OCH₃ 2 NH₄ a3-6 6′- 3′-OH 2 5-COOH 1 H a3-7 6′- 3′-Br 1 2-OC₂H₅ 1 Naa3-8 6′- 3′-OCH₃ 3 6-F 1 K a3-9 6′- 3′-iso-C₈H₁₇ 1 2-OCH₃ 1 Li a3-10 6′-3′-Br 1 2-tert-C₄H₉ 2 Na 5-tert-C₄H₉ a3-11 6′- 3′-iso-C₃H₇ 3 5-Br 1 Ka3-12 6′- H 2 5-I 1 H a3-13 6′- 3′-CH₃ 1 5-Cl 1 Li a3-14 6′- H 15-tert-C₄H₉ 1 H, Na a3-15 6′- H 1 H 1 H, Na a3-16 6′- H 2 5-tert-C₄H₉ 1H a3-17 6′- H 1 5-tert-C₄H₉ 1 H, Na a3-18 6′- H 1 5-CH₃ 1 NH₄ a3-19 6′-H 1 5-iso-C₈H₁₇ 1 K a3-20 6′- H 1 H 1 CH₃ a3-21 6′- H 1 H 1 C₂H₅ a3-226′- H 1 H 1 n-C₄H₉ a3-23 6′- 2′-CH₃ 1 5-tert-C₄H₉ 1 CH₃ a3-24 6′- H 15-iso-C₃H₇ 1 CH₃ a3-25 6′- H 1 5-Cl 1 n-C₃H₇ a3-26 6′- H 1 H 1 H, NH₄a3-27 6′- 3′-Br 1 2-OC₂H₅ 1 (C₄H₉)₄N

TABLE 4 (3-b)

Examples Substitution of Position of Chemical Vinyl Group R² g R¹ h Mb1-1 4′- H 1 H 1 H b1-2 4′- H 1 3-tert-C₄H₉ 1 H b1-3 4′- H 1 6-iso-C₈H₁₇1 H b1-4 4′- H 1 3-iso-C₃H₇ 1 H b1-5 4′- H 1 6-CH₃ 1 H b1-6 4′- 3′-OCH₃2 3-F 2 NH₄ 6-OCH₃ b1-7 4′- 3′-OH 2 6-COOH 1 H b1-8 4′- 2′-Br 1 2-OC₂H₅1 Na b1-9 4′- 3′-OCH₃ 3 6-F 1 K b1-10 4′- 3′-Cl 1 3-tert-OC₄H₉ 1 H, Nab1-11 4′- 3′-F 1 2-OCH₃ 1 Li b1-12 4′- 3′-tert-C₄H₉ 1 2-OH 2 NH₄ 3-CH₃b1-13 4′- 3′-iso-C₈H₁₇ 1 2-OCH₃ 1 H b1-14 4′- 3′-Br 1 3-tert-C₄H₉ 2 Na6-tert-C₄H₉ b1-15 4′- 3′-iso-C₃H₇ 3 3-Br 1 K b1-16 4′- H 2 3-I 1 H, Nab1-17 4′- 2′-CH₃ 1 3-Cl 1 Li b1-18 4′- H 1 H 1 H, Na b1-19 4′- H 13-tert-C₄H₉ 1 H, Na b1-20 4′- H 1 2-Br 1 Na b1-21 4′- H 1 2-Br 1 H b1-224′- H 1 2-Cl 1 H b1-23 4′- H 1 H 1 CH₃ b1-24 4′- H 1 H 1 C₂H₅ b1-25 4′-H 1 H 1 n-C₄H₉ b1-26 4′- H 1 3-iso-C₃H₇ 1 CH₃ b1-27 4′- H 1 3-Cl 1n-C₅H₁₁ b1-28 4′- 3′-OCH₃ 1 H 1 C₂H₅

TABLE 5 Exam- ples of Substitution Chem- Position of ical Vinyl Group R²g R¹ h M b2-1 5′- H 1 H 1 H b2-2 5′- H 1 3-tert-C₄H₉ 1 H b2-3 5′- H 13-iso-C₈H₁₇ 1 H b2-4 5′- H 1 3-iso-C₃H₇ 1 H, Na b2-5 5′- H 1 3-CH₃ 1 Hb2-6 5′- H 2 H 1 H b2-7 5′- 3′-OH 2 3-COONH₄ 1 NH₄ b2-8 5′- 4′-Br 12-OC₂H₅ 1 Na b2-9 5′- 4′-OCH₃ 3 6-F 1 K b2-10 5′- 6′-Cl 1 3-tert-OC₄H₉ 1H b2-11 5′- 2′-OC₂H₅ 1 2-OCH₃ 1 Li b2-12 5′- 3′-tert-C₄H₉ 1 2-OH 2 NH₄3-CH₃ b2-13 5′- H 1 H 1 H, Na b2-14 5′- H 1 3-Br 1 Na b2-15 5′- H 1 2-Br1 H b2-16 5′- H 1 3-tert-C₄H₉ 1 CH₃ b2-17 5′- H 1 H 1 C₂H₅ b2-18 5′- H 1H 1 n-C₄H₉ b2-19 5′- H 1 H 1 CH₃

TABLE 6 Exam- ples of Substitution Chem- Position of ical Vinyl Group R²g R¹ h M b3-1 6′- H 1 H 1 H b3-2 6′- H 1 3-tert-C₄H₉ 1 H b3-3 6′- H 13-iso-C₃H₇ 1 H, Na b3-4 6′- H 1 6-CH₃ 1 Li b3-5 6′- 3′-OCH₃ 2 3-C₂H₅ 2NH₄ 6-OCH₃ b3-6 6′- 2′-Br 1 2-OC₂H₅ 1 H, Na b3-7 6′- H 2 3-tert-C₄H₉ 1 Hb3-8 6′- 3′-tert-C₄H₉ 1 2-OH 2 NH₄ 3-CH₃ b3-9 6′- H 1 2-OCH₃ 1 H b3-106′- H 1 3-tert-C₄H₉ 2 Na 6-tert-C₄H₉ b3-11 6′- H 3 3-Br 1 K b3-12 6′- H2 H 1 H, Na b3-13 6′- 2′-CH₃ 1 3-Cl 1 Li b3-14 6′- H 1 H 1 H, Na b3-156′- 3′-iso-C₃H₇ 1 2-Br 1 Na b3-16 6′- H 1 2-Cl 1 H b3-17 6′- H 1 H 1 CH₃b3-18 6′- H 1 H 1 C₂H₅ b3-19 6′- 2′-CH₃ 1 3-iso-C₃H₇ 1 CH₃ b3-20 6′- H 13-Cl 1 n-C₅H₁₁

TABLE 7 (3-c)

Examples Substitution of Position of Chemical Vinyl Group R² g R¹ h Mc1-1 4′- H 1 H 1 H c1-2 4′- H 1 3-tert-C₄H₉ 1 H c1-3 4′- H 1 3-iso-C₈H₁₇1 H c1-4 4′- H 1 4-iso-C₃H₇ 1 H c1-5 4′- H 1 3-CH₃ 1 H c1-6 4′- H 2 H 1H c1-7 4′- 3′-iso-C₈H₁₇ 3 4-OH 1 K c1-8 4′- 2′-Br 2 2-F 2 H, Na 3-OCH₃c1-9 4′- 3′-iso-C₃H₇ 1 2-COOH 1 H c1-10 4′- 3′-OCH₃ 1 2-OC₂H₅ 1 Li c1-114′- 3′-Cl 1 ₄-Br 1 H c1-12 4′- 2′-F 1 3-tert-C₄H₉ 1 Na c1-13 4′-2′-tert-C₄H₉ 1 3-iso-C₃H₇ 1 K c1-14 4′- 2′-OC₂H₅ 1 4-OC₄H₉ 1 H c1-15 4′-2′-OCH₃ 3 H 1 H c1-16 4′- 2′-OC₂H₅ 2 3-n-C₄H₉ 1 NH₄ c1-17 4′- 2′-COONa 12-OCH₃ 1 Na c1-18 4′- 2′-tert-C₄H₉ 1 2-OH 1 K c1-19 4′- H 1 3-tert-C₄H₉1 H, Na c1-20 4′- H 1 3-iso-C₈H₁₇ 1 H, Na c1-21 4′- H 2 3-tert-C₄H₉ 1 Hc1-22 4′- H 1 3-CH₃ 1 NH₄ c1-23 4′- H 1 H 1 H, Na c1-24 4′- H 1 3-Cl 1 Hc1-25 4′- H 1 3-n-C₄H₉ 1 H c1-26 4′- H 1 H 1 CH₃ c1-27 4′- H 1 H 1 C₂H₅c1-28 4′- H 1 3-Cl 1 n-C₄H₉ c1-29 4′- H 1 3-tert-C₄H₉ 1 CH₃ c1-30 4′-2′-OC₂H₅ 1 H 1 C₂H₅

TABLE 8 Exam- ples of Substitution Chem- Position of ical Vinyl Group R²g R¹ h M c2-1 5′- H 1 H 1 H c2-2 5′- H 1 3-tert-C₄H₉ 1 H c2-3 5′- H 13-iso-C₈H₁₇ 1 H, Na c2-4 5′- H 1 3-iso-C₃H₇ 1 H c2-5 5′- H 1 3-CH₃ 1 Hc2-6 5′- H 1 2-C₂H₅ 1 NH₄ c2-7 5′- 4′-iso-C₈H₁₇ 3 4-OH 1 K c2-8 5′- H 2H 1 H c2-9 5′- 4′-Br 2 3-F 2 Li 2-OCH₃ c2-10 5′- 4′-iso-C₃H₇ 1 3-COONa 1Na c2-11 5′- 4′-OCH₃ 1 2-OC₂H₅ 1 Na c2-12 5′- 4′-Cl 1 3-Br 1 H c2-13 5′-6′-F 1 3-tert-C₄H₉ 1 Na c2-14 5′- 2′-OH 2 2-OH 2 NH₄ 4-CH₃ c2-15 5′- H 23-tert-C₄H₉ 1 H c2-16 5′- H 1 3-CH₃ 1 NH₄ c2-17 5′- H 1 H 1 H, Na c2-185′- H 1 3-Cl 1 H c2-19 5′- H 1 H 1 CH₃ c2-20 5′- H 1 H 1 C₂H₅ c2-21 5′-4′-CH₃ 1 H 1 iso-C₃H₇

TABLE 9 Exam- ples of Substitution Chem- Position of ical Vinyl Group R²g R¹ h M c3-1 6′- H 1 H 1 H c3-2 6′- H 1 3-tert-C₄H₉ 1 H c3-3 6′- H 13-iso-C₈H₁₇ 1 H c3-4 6′- H 2 H 1 H c3-5 6′- 3′-iso-C₈H₁₇ 3 4-OH 1 K c3-66′- H 2 2-F 2 H, Na 3-n-C₄H₉ c3-7 6′- 3′-iso-C₃H₇ 1 2-COOH 1 H c3-8 6′-3′-OCH₃ 1 2-OC₂H₅ 1 Li c3-9 6′- 3′-Cl 1 4-Br 1 H c3-10 6′- H 23-tert-C₄H₉ 1 Na c3-11 6′- 2′-tert-C₄H₉ 1 3-iso-C₃H₇ 1 K c3-12 6′- H 3 H1 H c3-13 6′- 2′-OC₂H₅ 2 3-n-C₄H₉ 1 NH₄ c3-14 6′- 2′-COONa 1 2-OCH₃ 1 Nac3-15 6′- 2′-tert-C₄H₉ 1 2-OH 1 K c3-16 6′- H 1 3-tert-C₄H₉ 1 H, Nac3-17 6′- H 2 3-tert-C₄H₉ 1 H c3-18 6′- H 1 3-CH₃ 1 NH₄ c3-19 6′- H 13-Cl 1 H c3-20 6′- H 1 H 1 CH₃ c3-21 6′- H 1 H 1 C₂H₅ c3-22 6′- H 1 3-Cl1 n-C₄H₉ c3-23 6′- H 1 3-C₂H₅ 1 CH₃

TABLE 10 (3-d)

Examples Substitution of Position of Chemical Vinyl Group R² g R¹ h Md1-1 4′- H 1 H 1 H d1-2 4′- H 3 H 1 H d1-3 4′- H 1 2-tert-C₄H₉ 1 H d1-44′- H 1 2-CH₃ 1 H d1-5 4′- H 1 2-iso-C₃H₇ 1 H d1-6 4′- H 1 2-tert-C₈H₁₇1 H d1-7 4′- H 1 2-Br 1 H d1-8 4′- 2′-Cl 1 2-CH₃ 1 H d1-9 4′- H 2 H 1 Hd1-10 4′- H 2 2-Cl 1 H d1-11 4′- 3′-OCH₃ 1 3-OCH₃ 1 Na d1-12 4′- H 1 H 1Na d1-13 4′- 3′-iso-C₃H₇ 1 2-OCH₃ 1 K d1-14 4′- 3′-OH 2 2-OC₂H₅ 1 NH₄d1-15 4′- 3′-iso-C₃H₇ 1 2-COOH 1 H, Na d1-16 4′- H 1 H 1 CH₃ d1-17 4′- H1 H 1 iso-C₃H₇

TABLE 11 Exam- ples of Substitution Chem- Position of ical Vinyl GroupR² g R¹ h M d2-1 5′- H 1 H 1 H d2-2 5′- H 1 2-tert-C₄H₉ 1 H d2-3 5′- H 12-CH₃ 1 H d2-4 5′- H 1 2-C₂H₅ 1 H d2-5 5′- H 1 2-iso-C₃H₇ 1 H d2-6 5′- H1 2-tert-C₈H₁₇ 1 H d2-7 5′- H 1 2-Br 1 H d2-8 5′- 4′-Cl 1 2-Cl 1 H d2-95′- H 2 2-OCH₃ 1 H d2-10 5′- 6′-Br 2 2-COOH 1 H, Na d2-11 5′-4′-iso-C₃H₇ 1 2-OC₂H₅ 1 Li d2-12 5′- 4′-OCH₃ 1 2-Br 2 Na 5-Br d2-13 5′-2′-Cl 3 2-F 3 H 5-F 2-F d2-14 5′- 6′-F 1 H 1 Na d2-15 5′- 4′-OH 12-tert-C₄H₉ 1 NH₄ d2-16 5′- H 1 H 1 CH₃ d2-17 5′- H 1 2-tert-C₄H₉ 1iso-C₃H₇

TABLE 12 Exam- ples of Substitution Chem- Position of ical Vinyl GroupR² g R¹ h M d3-1 6′- H 1 H 1 H d3-2 6′- H 1 2-tert-C₄H₉ 1 H d3-3 6′-4′-C₂H₅ 1 2-OC₂H₅ 1 H, Na d3-4 6′- H 1 2-Br 1 H d3-5 6′- H 1 H 1 C₂H₅d3-6 6′- H 1 2-tert-C₄H₉ 1 tert-C₄H₉

TABLE 13 (3-e)

Examples Substitution of Position of Chemical Vinyl Group R² g R¹ h Me1-1 4′- H 1 6-iso-C₃H₇ 1 H e1-2 4′- H 1 H 1 H e1-3 4′- 2′-OH 16-tert-C₄H₉ 1 H e1-4 4′- H 1 6-CH₃ 1 H e1-5 4′- H 1 6-Cl 1 H e1-6 4′- H1 6-tert-C₈H₁₇ 1 H e1-7 4′- H 1 6-Br 1 H e1-8 4′- 2′-Cl 1 6-Br 1 H e1-94′- H 2 H 1 H e1-10 4′- H 2 6-F 1 H e1-11 4′- 3′-OCH₃ 1 6-CH₃ 1 Na e1-124′- 3′-Cl 1 4-F 1 H e1-13 4′- 3′-iso-C₃H₇ 1 6-OCH₃ 1 K e1-14 4′- 3′-OH 26-OC₂H₅ 1 NH₄ e1-15 4′- 3′-iso-C₃H₇ 3 6-COOH 1 H, Na e1-16 4′- H 1 H 1Na e1-17 4′- 3′-OC₃H₇ 1 6-OC₂H₅ 1 H e1-18 4′- H 1 H 1 n-C₄H₉ e1-19 4′- H1 H 1 CH₃

TABLE 14 Exam- ples of Substitution Chem- Position of ical Vinyl GroupR² g R¹ h M e2-1 5′- H 1 H 1 H e2-2 5′- H 1 6-CH₃ 1 H e2-3 5′- H 16-iso-C₃H₇ 1 H e2-4 5′- H 1 6-tert-C₈H₁₇ 1 H e2-5 5′- H 1 6-Br 1 H e2-65′- H 1 6-Cl 1 H e2-7 5′- H 1 6-F 1 H e2-8 5′- H 2 H 1 H e2-9 5′- H 26-iso-C₃H₇ 1 H e2-10 5′- H 3 H 1 H e2-11 5′- 4′-iso-C₈H₁₇ 1 4-OH 1 Nae2-12 5′- H 2 2-F 3 H 4-F 6-F e2-13 5′- 6′-Br 2 6-F 2 K 4-OCH₃ e2-14 5′-6′-F 1 6-tert-C₄H₉ 1 NH₄ e2-15 5′- 4′-OCH₃ 1 2-OC₂H₅ 1 H, Na e2-16 5′- H1 6-n-C₄H₉ 1 NH₄ e2-17 5′- H 1 H 1 CH₃

TABLE 15 Exam- ples of Substitution Chem- Position of ical Vinyl GroupR² g R¹ h M e3-1 6′- H 1 H 1 H e3-2 6′- H 2 H 1 H, Na e3-3 6′- H 16-iso-C₃H₇ 1 H e3-4 6′- 2′-OH 1 6-tert-C₄H₉ 1 NH₄ e3-5 6′- H 1 H 1 C₂H₅

TABLE 16 (3-f)

Substitution Examples of Position of Chemical Vinyl Group R² g R¹ h Mf1-1 4′- H 1 5-tert-C₄H₉ 1 H f1-2 4′- H 1 5-CH₃ 1 H f1-3 4′- H 15-iso-C₃H₇ 1 H f1-4 4′- H 1 5-tert-C₈H₁₇ 1 H f1-5 4′- H 1 5-Br 1 H f1-64′- 2′-Cl 1 5-CH₃ 1 H f1-7 4′- H 2 5-Cl 1 H f1-8 4′- 3′-OCH₃ 1 5-OCH₃ 2Na f1-9 4′- 3′-Cl 3 5-F 2 H f1-10 4′- 3′-iso-C₃H₇ 1 5-OCH₃ 2 K f1-11 4′-3′-OH 2 5-OC₂H₅ 2 NH₄ f1-12 4′- 3′-iso-C₃H₇ 1 5-COOH 2 H, Na f1-13 4′- H1 5-iso-C₃H₇ 1 C₂H₅

TABLE 17 Exam- ples of Substitution Chem- Position of ical Vinyl GroupR² g R¹ h M f2-1 5′- H 1 5-tert-C₄H₉ 1 H f2-2 5′- H 1 5-CH₃ 1 H f2-3 5′-H 1 5-C₂H₅ 1 H, Na f2-4 5′- H 1 5-iso-C₃H₇ 1 H f2-5 5′- H 1 5-tert-C₈H₁₇1 H f2-6 5′- H 1 5-Br 1 H f2-7 5′- H 2 5-OCH₃ 1 H f2-8 5′- 4′-Br 25-COOH 1 H, Na f2-9 5′- 4′-iso-C₃H₇ 1 5-OC₂H₅ 1 Li f2-10 5′- 6′-Cl 15-tert-C₄H₉ 1 NH₄ f2-11 5′- H 1 5-tert-C₄H₉ 1 CH₃

TABLE 18 Exam- ples of Substitution Chem- Position of ical Vinyl GroupR² g R¹ h M f3-1 6′- H 1 5-tert-C₄H₉ 1 H f3-2 6′- H 1 5-C₂H₅ 1 H, Naf3-3 6′- H 1 5-iso-C₃H₇ 1 H f3-4 6′- 3′-iso-C₃H₇ 1 5-OCH₃ 2 K f3-5 6′- H1 5-iso-C₃H₇ 1 n-C₃H₇

In Tables 1-18, if the substituent R¹ is exclusively hydrogen atom, thenH is entered, and if anything other than hydrogen atom is included, thesubstituent(s) other than hydrogen atom is entered. Also, where thesubstituent R¹ is exclusively hydrogen atom, the value of h is 1, andotherwise the value entered for h is the number of the substituentsminus the number of substituent hydrogen atom(s).

These styrene derivatives can be synthesized with ease by means of anyknown method, such as Williamson reaction, which is described in page187 of The 4^(th) Series of Experimental Chemistry (edited by TheChemical Society of Japan and published by Maruzen Co., Ltd.).

The step of synthesizing a styrene derivative is conducted, for example,by a reaction in a solvent between a substituted or non-substitutedvinyl phenyl alkyrene halide and a substituted or non-substituteddihydroxy aromatic carboxylic acid and its alkyl ester, preferably ahydroxy salicylic acid and its alkyl ester. An example is shown infollowing Reaction Formula (7). In the reaction between a substituted ornon-substituted vinyl phenyl alkyrene halide and a substituted ornon-substituted dihydroxy aromatic carboxylic acid, it is possible toselect one kind each of the reactants or select mixtures of two or morekinds each of the reactants. It is also possible to obtain an alkylester of a styrene derivative by reacting, by means of a known method, astyrene derivative in which M of the —COOM group is a hydrogen atom oran alkaline metal with an alcohol having 1-18 carbon atoms, for example.As the alcohol having 1-18 carbon atoms, specific examples includemethanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol,tert-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol,1-ethylhexanol, 2-ethylhexanol, 1-nonyl alcohol and 1-decyl alcohol.Among these, methanol, ethanol, n-propanol, isopropanol, n-butanol,isobutanol and tert-butanol are preferable for the reasons of easyavailability and high reactivity.

In the Reaction Formula (7), R¹, R², M, h and g are the same as above,and X is a halogen atom such as F, Cl and Br.

The substituted or non-substituted vinyl phenyl alkylene halide isspecifically exemplified by:

-   p-(halogen-containing-methyl)styrene derivatives such as    4-(chloromethyl)styrene, 4-(bromomethyl)styrene,    3-methoxy-4-(chloromethyl)styrene, 3-methoxy-4-(bromomethyl)styrene,    2-hydroxy-4-(chloromethyl)styrene, 2-hydroxy-4-(bromomethyl)styrene,    3-bromo-4-(chloromethyl)styrene, 3-bromo-4-(bromomethyl)styrene,    2-methoxy-4-(chloromethyl)styrene, 2-methoxy-4-(bromomethyl)styrene,    2-chloro-4-(chloromethyl)styrene, 2-chloro-4-(bromomethyl)styrene,    3-fluoro-4-(chloromethyl)styrene, 3-fluoro-4-(bromomethyl)styrene,    2-bromo-4-(chloromethyl)styrene, 2-bromo-4-(bromomethyl)styrene,    3-tert-butyl-4-(chloromethyl)styrene,    3-tert-butyl-4-(bromomethyl)styrene,    3-isooctyl-4-(chloromethyl)styrene,    3-isooctyl-4-(bromomethyl)styrene,    3-isopropyl-4-(chloromethyl)styrene,    3-isopropyl-4-(bromomethyl)styrene,    3-methyl-4-(chloromethyl)styrene, 3-methyl-4-(bromomethyl)styrene,    3-ethoxy-4-(chloromethyl)styrene, 3-ethoxy-4-(bromomethyl)styrene,    3-carboxy-4-(chloromethyl)styrene, and    3-carboxy-4-(bromomethyl)styrene;-   m-(halogen-containing-methyl)styrene derivatives such as    3-(chloromethyl)styrene, 3-(bromomethyl)styrene,    5-methyl-3-(chloromethyl)styrene, 5-methyl-3-(bromomethyl)styrene,    5-isopropyl-3-(chloromethypstyrene,    5-isopropyl-3-(bromomethyl)styrene,    5-isooctyl-3-(chloromethyl)styrene,    5-isooctyl-3-(bromomethyl)styrene,    5-methoxy-3-(chloromethyl)styrene, 5-methoxy-3-(bromomethyl)styrene,    4-ethoxy-3-(chloromethyl)styrene, 4-ethoxy-3-(bromomethyl)styrene,    4-carboxy-3-(chloromethyl)styrene, 4-carboxy-3-(bromomethyl)styrene,    5-hydroxy-3-(chloromethyl)styrene, 5-hydroxy-3-(bromomethyl)styrene,    4-hydroxy-3-(chloromethyl)styrene, 4-hydroxy-3-(bromomethyl)styrene,    4-methoxy-3-(chloromethyl)styrene, 4-methoxy-3-(bromomethyl)styrene,    5-chloro-3-(chloromethyl)styrene, 5-chloro-3-(bromomethyl)styrene,    4-bromo-3-(chloromethyl)styrene, 4-bromo-3-(bromomethyl)styrene,    2-bromo-3-(chloromethyl)styrene, 2-bromo-3-(bromomethyl)styrene,    5-tert-butyl-3-(chloromethyl)styrene, and    5-tert-butyl-3-(bromomethyl)styrene;-   o-(halogen-containing-methyl)styrene derivatives such as    2-(chloromethyl)styrene, 2-(bromomethyl)styrene,    3-tert-butyl-2-(chloromethyl)styrene,    3-tert-butyl-2-(bromomethyl)styrene,    4-chloro-2-(chloromethyl)styrene, and    4-chloro-2-(bromomethyl)styrene;-   p-(halogen-containing-ethyl)styrene derivatives such as    4-(2′-bromoethyl)styrene, 4-(2′-chloroethyl)styrene,    3-methoxy-4-(2′-bromoethyl)styrene,    3-methoxy-4-(2′-chloroethyl)styrene,    2-hydroxy-4-(2′-bromoethyl)styrene,    2-hydroxy-4-(2′-chloroethyl)styrene,    3-ethoxy-4-(2′-bromoethyl)styrene,    3-ethoxy-4-(2′-chloroethyl)styrene,    3-bromo-4-(2′-bromoethyl)styrene, 3-bromo-4-(2′-chloroethyl)styrene,    3-tert-butyl-4-(2′-bromoethyl)styrene, and    3-tert-butyl-4-(2′-chloroethyl)styrene;-   m-(halogen-containing-ethyl)styrene derivatives such as    3-(2′-bromoethyl)styrene, 3-(2′-chloroethyl)styrene,    5-isopropyl-3-(2′-bromoethyestyrene,    5-isopropyl-3-(2′-chloroethyl)styrene,    5-chloro-3-(2′-bromoethyl)styrene,    5-chloro-3-(2′-chloroethyl)styrene,    5-hydroxy-3-(2′-bromoethyl)styrene,    5-hydroxy-3-(2′-chloroethyl)styrene,    4-hydroxy-3-(2′-bromoethyl)styrene,    4-hydroxy-3-(2′-chloroethyl)styrene,    4-bromo-3-(2′-bromoethyl)styrene, and    4-bromo-3-(2′-chloroethyl)styrene;-   o-(halogen-containing-ethyl)styrene derivatives such as    2-(2′-bromoethyl)styrene, 2-(2′-chloroethyl)styrene,    3-tert-butyl-2-(2′-bromoethyl)styrene, and    3-tert-butyl-2-(2′-chloroethyl)styrene;-   p-(halogen-containing-propyl)styrene derivatives such as    4-(3′-bromopropyl)styrene, 4-(3′-chloropropyl)styrene,    2-methoxy-4-(3′-bromopropyl)styrene,    2-methoxy-4-(3′-chloropropyl)styrene,    2-isopropyl-4-(3′-bromopropyl)styrene,    2-isopropyl-4-(3′-chloropropyl)styrene,    2-isooctyl-4-(3′-bromopropyl)styrene,    2-isooctyl-4-(3′-chloropropyl)styrene,    3-methoxy-4-(3′-bromopropyl)styrene, and    3-methoxy-4-(3′-chloropropyl)styrene;-   m-(halogen-containing-propyl)styrene derivatives such as    3-(3′-bromopropyl)styrene, 3-(3′-chloropropyl)styrene,    5-isooctyl-3-(3′-bromopropyl)styrene,    5-isooctyl-3-(3′-chloropropyl)styrene,    5-methoxy-3-(3′-bromopropyl)styrene,    5-methoxy-3-(3′-chloropropyl)styrene, and 2-(3′-bromopropyl)styrene;-   and o-(halogen-containing-propyl)styrene derivatives such as    2-(3′-chloropropyl)styrene.

The substituted or non-substituted dihydroxy aromatic carboxylic acid isspecifically exemplified by:

-   2,3-dihydroxy benzoic acid derivatives and their alkyl esters having    1-18 carbon atoms such as 2,3-dihydroxy benzoic acid,    5-methyl-2,3-dihydroxy benzoic acid, 5-ethyl-2,3-dihydroxy benzoic    acid, 5-isopropyl-2,3-dihydroxy benzoic acid,    5-n-butyl-2,3-dihydroxy benzoic acid, 5-tert-butyl-2,3-dihydroxy    benzoic acid, 5-sec-butyl-2,3-dihydroxy benzoic acid,    5-isoheptyl-2,3-dihydroxy benzoic acid, 5-isohexyl-2,3-dihydroxy    benzoic acid, 5-isooctyl-2,3-dihydroxy benzoic acid,    5-fluoro-2,3-dihydroxy benzoic acid, 5-chloro-2,3-dihydroxy benzoic    acid, 5-bromo-2,3-dihydroxy benzoic acid,    5-fluoro-4-methoxy-2,3-dihydroxy benzoic acid, 4-ethyl-2,3-dihydroxy    benzoic acid, 4-methoxy-2,3-dihydroxy benzoic acid,    4-ethoxy-2,3-dihydroxy benzoic acid, 2,3,4-trihydroxy benzoic acid,    4-fluoro-5-methoxy-2,3-dihydroxy benzoic acid,    6-isopropyl-2,3-dihydroxy benzoic acid, and 6-butoxy-2,3-dihydroxy    benzoic acid;-   2,4-dihydroxy benzoic acid derivatives and their alkyl esters having    1-18 carbon atoms such as 2,4-dihydroxy benzoic acid,    6-methyl-2,4-dihydroxy benzoic acid, 6-ethyl-2,4-dihydroxy benzoic    acid, 6-isopropyl-2,4-dihydroxy benzoic acid,    6-tert-butyl-2,4-dihydroxy benzoic acid, 6-sec-butyl-2,4-dihydroxy    benzoic acid, 6-isohexyl-2,4-dihydroxy benzoic acid,    6-isoheptyl-2,4-dihydroxy benzoic acid, 6-isooctyl-2,4-dihydroxy    benzoic acid, 5-methoxy-2,4-dihydroxy benzoic acid,    6-butoxy-2,4-dihydroxy benzoic acid, 6-chloro-2,4-dihydroxy benzoic    acid, 6-bromo-2,4-dihydroxy benzoic acid, 6-iodo-2,4-dihydroxy    benzoic acid, 5-n-propyl-2,4-dihydroxy benzoic acid,    5-ethoxy-2,4-dihydroxy benzoic acid, 5-chloro-2,4-dihydroxy benzoic    acid, 5-bromo-2,4-dihydroxy benzoic acid, 6-methyl-2,4,5-trihydroxy    benzoic acid, 5,6-di-tert-butyl-2,4-dihydroxy benzoic acid,    3-tert-butyl-2,4-dihydroxy benzoic acid, 3-isooctyl-2,4-dihydroxy    benzoic acid, 3-chloro-2,4-dihydroxy benzoic acid,    3-fluoro-2,4-dihydroxy benzoic acid, and 3-bromo-2,4-dihydroxy    benzoic acid;-   2,5-dihydroxy benzoic acid derivatives and their alkyl esters having    1-18 carbon atoms such as 2,5-dihydroxy benzoic acid,    3-methyl-2,5-dihydroxy benzoic acid, 3-ethyl-2,5-dihydroxy benzoic    acid, 3-isopropyl-2,5-dihydroxy benzoic acid,    3-tert-butyl-2,5-dihydroxy benzoic acid, 3-sec-butyl-2,5-dihydroxy    benzoic acid, 3-isohexyl-2,5-dihydroxy benzoic acid,    3-isoheptyl-2,5-dihydroxy benzoic acid, 3-isooctyl-2,5-dihydroxy    benzoic acid, 3-tert-butoxy-2,5-dihydroxy benzoic acid,    3-chloro-2,5-dihydroxy benzoic acid, 3-bromo-2,5-dihydroxy benzoic    acid, 3-iodo-2,5-dihydroxy benzoic acid, 3-fluoro-2,5-dihydroxy    benzoic acid, 6-methoxy-2,5-dihydroxy benzoic acid,    6-ethoxy-2,5-dihydroxy benzoic acid, 3-methyl-2,5,6-trihydroxy    benzoic acid, 6-fluoro-4-methoxy-2,5-dihydroxy benzoic acid,    3,4-diisopropyl-2,5-dihydroxy benzoic acid,    3,4-di-tert-butyl-2,5-dihydroxy benzoic acid,    4-chloro-3-tert-butyl-2,5-dihydroxy benzoic acid, and    4-fluoro-2,5-dihydroxy benzoic acid;-   2,6-dihydroxy benzoic acid derivatives and their alkyl esters having    1-18 carbon atoms such as 2,6-dihydroxy benzoic acid,    3-bromo-2,6-dihydroxy benzoic acid, 4-bromo-2,6-dihydroxy benzoic    acid, 5-bromo-2,6-dihydroxy benzoic acid, 3-chloro-2,6-dihydroxy    benzoic acid, 4-chloro-2,6-dihydroxy benzoic acid,    5-chloro-2,6-dihydroxy benzoic acid, 3-isopropyl-2,6-dihydroxy    benzoic acid, 4-tert-butyl-2,6-dihydroxy benzoic acid, and    5-methyl-2,6-dihydroxy benzoic acid;-   4,5-dihydroxy benzoic acid derivatives and their alkyl esters having    1-18 carbon atoms such as 3-methyl-4,5-dihydroxy benzoic acid,    3-tert-butyl-4,5-dihydroxy benzoic acid, 3-tert-octyl-4,5-dihydroxy    benzoic acid, 3-ethoxy-4,5-dihydroxy benzoic acid,    3-methoxy-4,5-dihydroxy benzoic acid, and 3-chloro-4,5-dihydroxy    benzoic acid;-   3,5-dihydroxy benzoic acid derivatives and their alkyl esters having    1-18 carbon atoms such as 3,5-dihydroxy benzoic acid,    4-methyl-3,5-dihydroxy benzoic acid, 4-isopropyl-3,5-dihydroxy    benzoic acid, 4-tert-butyl-3,5-dihydroxy benzoic acid,    4-ethoxy-3,5-dihydroxy benzoic acid, and 4-butoxy-3,5-dihydroxy    benzoic acid; and-   3,4-dihydroxy benzoic acid derivatives and their alkyl esters having    1-18 carbon atoms such as 3,4-dihydroxy benzoic acid,    2,3,4-trihydroxy benzoic acid, 6-fluoro-3,5-dihydroxy benzoic acid,    5-methyl-3,4-dihydroxy benzoic acid, 5-isopropyl-3,4-dihydroxy    benzoic acid, 5-tert-butyl-3,4-dihydroxy benzoic acid,    5-tert-octyl-3,4-dihydroxy benzoic acid, 5-methoxy-3,4-dihydroxy    benzoic acid, 5-ethoxy-3,4-dihydroxy benzoic acid,    5-bromo-3,4-dihydroxy benzoic acid, 5-chloro-3,4-dihydroxy benzoic    acid, 6-methoxy-3,4-dihydroxy benzoic acid, 6-n-propyl-3,4-dihydroxy    benzoic acid, and 6-n-butyl-3,4-dihydroxy benzoic acid.

Possible examples of reaction solvent include organic solvents such as:alcohols, ethers and glycols exemplified by methanol, ethanol,isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethylether, propylene glycol monomethyl ether, ethylene glycol dimethyl ether(monoglyme), diethylene glycol dimethyl ether (diglyme), ethylene glycoldiethyl ether, triethylene glycol dimethyl ether (triglyme),tetraethylene glycol dimethyl ether (tetraglyme), ethylene glycol, andpropylene glycol; aprotic organic polar solvents exemplified byN,N-dimethylformamide (DMF), N,N-dimethylacetamide,N-methyl-2-pyrrolidone, and dimethyl sulfoxide; ketones exemplified byacetone, methyl ethyl ketone, and methyl isobutyl ketone; estersexemplified by ethyl acetate, butyl acetate, ethyl propionate, andcellosolve acetate; hydrocarbons exemplified by hexane, octane,petroleum ether, cyclohexane, benzene, toluene, and xylene; andhalogenated hydrocarbons exemplified by trichloroethylene,dichloromethane, and chloroform.

In the reaction to synthesize the styrene derivative used in the presentinvention, it is preferable to add a base on the occasion of reactionpromotion and ether linking so as to trap hydrogen halide which isgenerated as a by-product.

The base that can be used for this synthesis may be any base so long asit does not complicate the reaction system by acting with a solvent or asubstrate. Examples include: hydroxides of alkaline metals such aslithium hydroxide, sodium hydroxide, and potassium hydroxide; carbonatesof alkaline metals such as lithium carbonate, sodium carbonate,potassium carbonate, cesium carbonate, and rubidium carbonate; andhydrides of alkaline metals such as lithium hydride, sodium hydride, andpotassium hydride.

The method A, which is one of the methods for manufacturing the chargecontrol resin of the present invention, can use, as a starting monomer,a vinyl group-containing monomer as well as the charge control monomer,which is the styrene derivative represented by the Formula (3). Apreferable method is such that a polymer is obtained by effecting apolymerization among monomers, in a solvent, within a reaction systemconsisting of the monomers comprising at least the charge controlmonomer and the vinyl group-containing monomer, which becomes theconstituent unit represented by the Formula (2), and a polymerizationinitiator. An example of this reaction system is represented byfollowing Reaction Formula (8).Styrene Derivative (Monomer) Represented by Formula (3)+Monomerα+(Monomer β+Monomer γ)+Polymerization Initiator→Polymer  (8)

In Formula (8), the monomers α, β, γ are monomers other than the styrenederivative represented by Formula (3), and are mutually different vinylgroup-containing monomers.

Examples of the vinyl group-containing monomer include: vinyl aromatichydrocarbon-containing monomers such as styrene, α-methylstyrene,p-methylstyrene, p-tert-butylstyrene, and p-chlorostyrene; (meth)acrylicacid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate,n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl(meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate,n-pentyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl(meth)acrylate, 3-(methyl)butyl (meth)acrylate, hexyl (meth)acrylate,2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl(meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl(meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, glycidyl(meth)acrylate, β-methacryloyloxy ethylhydrogen phthalate; monofunctional vinyl group-containing monomers such as vinyl chloride, vinylacetate, vinyl benzoate, vinyl methyl ethyl ketone, vinyl hexyl ketone,vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, and vinyltoluene; bifunctional vinyl group-containing monomers such as divinylbenzene and diethylene glycol (meth)acrylate; and monomers having threeor more reactive vinyl groups. It is possible to use any of thesemonomers singly or in a combination of two or more.

Preferable examples for the vinyl group-containing monomer are vinylaromatic hydrocarbon-containing monomers represented by the followingFormula (4). Examples for the vinyl aromatic hydrocarbon-containingmonomers include ones represented by the Formula (4). By polymerizingthis vinyl group-containing monomer, a constituent unit represented bythe Formula (2) is obtained.

In the Formula (4), R³, R⁴, R⁵ are independent of one another, and are ahydrogen atom, an alkyl group, a halogen atom, or an alkoxy group.

Examples of the substituents R³, R⁴ and R⁵ in the case wherein they arestraight-chained or branched alkyl groups having 1-8 carbon atomsinclude methyl group, ethyl group, propyl group, isopropyl group,n-butyl group, isobutyl group, sec-butyl group, tert-butyl group,n-pentyl group, isopentyl group, hexyl group, heptyl group, and octylgroup.

Examples of the substituents R³, R⁴ and R⁵ in the case wherein they arestraight-chained or branched alkoxy groups having 1-8 carbon atomsinclude methoxy group, ethoxy group, n-propoxy group, isopropoxy group,n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group,n-pentoxy group, isopentoxy group, hexyloxy group, heptoxy group, andoctyl-oxy group.

Examples of the substituents R³, R⁴ and R⁵ in the case wherein they arehalogen atoms include F, Cl and Br.

Examples of the vinyl aromatic hydrocarbon include styrene,α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene,2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-propylstyrene,3-propylstyrene, 4-propylstyrene, 2-isopropylstyrene,3-isopropylstyrene, 4-isopropylstyrene, 2-chlorostyrene,3-chlorostyrene, 4-chlorostyrene, 2-methyl-α-methylstyrene,3-methyl-α-methylstyrene, 4-methyl-α-methylstyrene,2-ethyl-α-methylstyrene, 3-ethyl-α-methylstyrene,4-ethyl-α-methylstyrene, 2-propyl-α-methylstyrene,3-propyl-α-methylstyrene, 4-propyl-α-methylstyrene,2-isopropyl-α-methylstyrene, 3-isopropyl-α-methylstyrene,4-isopropyl-α-methylstyrene, 2-chloro-α-methylstyrene,3-chloro-α-methylstyrene, 4-chloro-α-methylstyrene, 2,3-dimethylstyrene,3,4-dimethylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene,2,3-diethylstyrene, 3,4-diethylstyrene, 2,4-diethylstyrene,2,5-diethylstyrene, 2-methyl-3-ethylstyrene, 2-methyl-4-ethylstyrene,2-chloro-4-methylstyrene, 2,3-dimethyl-α-methylstyrene,3,4-dimethyl-α-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethyl-α-methylstyrene, 2,3-diethyl-α-methyl styrene, 3,4-diethyl-α-methyl styrene,2,4-diethyl-α-methylstyrene, 2,5-diethyl-α-methylstyrene,2-ethyl-3-methyl-α-methylstyrene, 2-methyl-4-propyl-α-methylstyrene,2-chloro-4-ethyl-α-methylstyrene, 2-methoxystyrene, 3-ethoxystyrene,4-ethoxystyrene, and 2-isoproxy styrene. These vinyl aromatichydrocarbon-containing monomers can be used singly or in combination oftwo or more.

The vinyl aromatic hydrocarbon-containing monomer is preferably astyrene. Following Formula (9) represents a constituent unit obtainedfrom such styrene.

An example for the vinyl group-containing monomer to be used in thepresent invention is a hydrophilic unsaturated monomer. Examples ofhydrophilic unsaturated monomer includes (meth)acrylic acid(s);(meth)acrylic acid alkyl esters such as hydroxyethyl (meth)acrylate,hydroxypropyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate;(meth)acrylamides such as (meth)acrylamide, N-methylol (meth)acrylamide,diacetone (meth)acrylamide, N-isopropyl (meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, andN,N-dimethyl(meth)acrylamide; alkyl(meth)acrylamide sulfonates or theiresters such as ethyl(meth)acrylamide sulfonic acid(s),propyl(meth)acrylamide sulfonic acid(s),tert-butyl-(meth)acrylamidesulfonic acid(s); styrene sulfonic acid(s),metallyl sulfonic acid(s), acryloyl morpholine, acrylonitrile, monobutylmaleate, isobutyl maleate, itaconic acid, and fumaric acid. Thesemonomers can be used singly or in combination of two or more of them. Ofthese monomers more preferred are (meth)acrylic acid(s), (meth)acrylicacid alkyl esters, tert-butyl-acrylamidesulfonic acid(s), and styrenesulfonic acid(s). It is noted that what is meant by (meth)acrylic acidis acrylic acids or methacrylic acids (i.e., α-methyl acrylic acid,which is an α-methyl derivative of acrylic acid). It is also noted thatacid(s) is meant to include the free acids and the metal salts, theammonium salt, and the alkyl esters of these acids, respectively.

The above-mentioned (meth)acrylic acid alkyl esters, acrylic acids andtheir salts, methacrylic acid (that is, α-methyl acrylic acid, which isan α-methyl derivative of acrylic acid), and their salts, and theiralkyl esters with hydrophilic group substituted are usable as the vinylgroup-containing monomer. These compounds are represented by thefollowing Formula (10).

In the Formula (10), R⁶ is either a methyl group or a hydrogen atom andR⁷ is either a hydroxyl group or an alkoxy group with or without asubstituent.

Examples of R⁷ in the case of the alkoxy group with or without asubstituent include methoxy group, ethoxy group, n-propoxy group,isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group,tert-butoxy group, n-pentoxy group, isopentoxy group, hexyl group,heptoxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group,and steary oxy group. Examples of a substituent that may be bonded tothe alkoxy group include hydroxyl group, carboxyl group and alkoxygroup.

Following Formula (11) represents a constituent unit obtained from thecompound represented by the Formula (10).

In the Formula (11), R⁶ and R⁷ are the same as above.

Table 19 shows specific examples of polymers which each have at leastthe constituent unit being obtained from the styrene derivative as themonomer represented by the Formula (3) or the Formula (6), and theconstituent unit obtained from a vinyl group-containing monomer. Thescope of the present invention shall not be limited by these examples.

TABLE 19 Examples Constituent Unit Obtained Constituent Unit ConstituentUnit Constituent Unit of from Styrene Derivative of Obtained fromObtained from Obtained from Polymer Formula (3) or Formula (6) Monomer αMonomer β Monomer γ 1 Formula (1) — Formula (9) — — 2 Formula (1) —Formula (9) Formula (2) — 3 Formula (1) — Formula (9) Formula (11) — 4Formula (1) — Formula (9) Formula (11) Formula (11′) 5 Formula (1) —Formula (2) — — 6 Formula (1) — Formula (2) Formula (11) — 7 Formula (1)— Formula (2) Formula (2′) — 8 Formula (1) — Formula (2) Formula (2′)Formula (11) 9 Formula (1) — Formula (11) — — 10 Formula (1) — Formula(11) Formula (11′) — 11 Formula (5) — Formula (9) Formula (2) — 12Formula (5) — Formula (9) Formula (11) — 13 Formula (5) — Formula (2) —14 Formula (5) — Formula (2) Formula (11) — 15 Formula (5) Formula (5″)Formula (9) — — 16 Formula (5″) — Formula (9) Formula (2) — 17 Formula(1) Formula (1″) Formula (2) — — 18 Formula (1″) — Formula (2) Formula(11) — 19 Formula (1) Formula (1′) Formula (2) — — 20 Formula (1″) —Formula (2) Formula (11) Formula (11′)

In Table 19, styrene derivatives and monomers α, η and γ arerespectively vinyl group-containing monomers different from each other.Also, the Formula (1) and Formula (1′), the Formula (2) and Formula(2′), and the Formula (11) and Formula (11′), respectively, representcompounds represented by the Formulae (1), (2) and (11) withsubstituents differed in the chemical structure. Also, in the Formula(1″) and Formula (5″), the COOM groups have been changed to alkylesters.

The method employed to effect the polymerization may be any of knownones such as solution polymerization, suspension polymerization,emulsion polymerization, dispersion polymerization, precipitationpolymerization and bulk polymerization. It is not limited

The solution polymerization is one of the methods used on an occasion ofeffecting a radical polymerization with a vinyl group-containing monomersuch as the styrene derivative represented by the Formula (3). In thismethod, the monomer and polymerization initiator are dissolved in asolvent wherein the product polymer is soluble, and the polymerizationis conducted by heating the solution. The polymerization initiator to beused can be benzoyl peroxide, azobis-isobutyronitrile or the like, whichare soluble in the monomer or the solvent. The solution polymerizationis characterized as providing lower degree of polymerization and lowerpolymerization velocity compared with the bulk polymerization, and sincethe heat of polymerization created in the polymerization system isremoved by the surrounding solvent, it is easy to control thepolymerization temperature. The solution polymerization is quiteuser-friendly if the solution is directly used as the polymer solutionafter the polymerization, but if the polymer is to be taken out in solidform, it is necessary to first remove the solvent and then recover thepolymer.

The bulk polymerization is one of the methods to carry out a radicalpolymerization of monomers having a vinyl group such as the styrenederivative represented by the Formula (3). It is a method to effectpolymerization without using a solvent but with heat between vinylmonomers by themselves or with a help of a small amount of apolymerization initiator. As the initiator, benzoyl peroxide orazobis-isobutyronitrile, which are soluble in the monomer is used. Thebulk polymerization is characteristic in that the polymerizationvelocity is large and that a relatively pure polymer is obtained inblocks. The problems with this reaction are that it is difficult toremove the polymerization heat so that localized heating takes placerendering it hard to control the polymerization temperature, and thatthe produced polymer solidifies and sticks to the vessel rendering ithard to restore the vessel, etc. Therefore after-treatments arecomplicated. Industrially, the bulk polymerization is adopted in makingof polystyrene pellet by continuous bulk polymerization from styrenemonomers, which is a styrene-containing resin like the one of thepresent invention, in making of organic glass frompolymethylmethacrylate, in hardening of glass fiber-reinforcedunsaturated polyester, in polymerization-casting in a metal mold(casting polymerization), etc.

The precipitation polymerization is one of the methods used on anoccasion of conducting a radical polymerization of monomers having avinyl group such as the styrene derivative represented by the Formula(3). It is a method wherein a solvent is used which dissolves themonomer and the initiator, but does not dissolve or swell the productpolymer almost, and wherein the polymerization is accompanied byheating. As the initiator, benzoyl peroxide or azobisisobutyronitrile orthe like is used, which are soluble in the monomer or the solvent. Asthe polymerization proceeds and the polymer is produced, it precipitatesas it is not soluble in the solvent. The precipitation polymerization ischaracteristic in that, as the polymerization proceeds and the producedpolymer precipitates, the produced polymer is substantially similar tothat of the bulk polymerization so that, in comparison to the solutionpolymerization, although the resulting polymerization degree andpolymerization velocity are higher, the controlling of thepolymerization temperature is easier because the polymerization heatwhich occurs in the polymerization system is removed by the surroundingsolvent. With the precipitation polymerization, it is possible to obtainthe polymer after the polymerization by merely isolating and drying, andthus it is possible to dispense with the use of suspension stabilizer oremulsifier which are used in suspension polymerization or emulsionpolymerization, and thus pure polymer can be obtained.

The suspension polymerization is one of the methods used on an occasionof conducting a radical polymerization of monomers having a vinyl groupsuch as the styrene derivative represented by the Formula (3). When amonomer insoluble to a medium (chiefly, water) is agitated intensely inthe medium, dispersion and suspension take place and a droplet having asize of 0.01-1 mm is made. To this if a polymerization initiator solubleto the monomer (for example, benzoyl peroxide andazobisisobutyronitrile) is added, then the suspension polymerizationproceeds. It is possible to conduct a polyaddition reaction in asuspended system, like in the case of polyurethane. In this polyadditionreaction, polymerization proceeds in the droplet of the monomer and agranular polymer is obtained. When a suspension polymerization iseffected using vinyl acetate, styrene or methyl methacrylate as themonomer, for example, true spherical particles are obtained so that suchoccasion is called as pearl polymerization. The polymerization withinthe droplet proceeds fundamentally in the same manner as the bulkcopolymerization, and the polymerization velocity and the polymerizationdegree are high. In the suspension polymerization, as the polymerizationproceeds, the droplet of the monomer becomes a solution rich in thesolute, which is the polymer, in the solvent, which is the monomer, toan extent such that the droplets are easy to unite with each other.Therefore, it is necessary to conduct this polymerization while givingan intense agitation so as to maintain thorough dispersion, and in orderto stabilize the droplets, a water-soluble polymer such as gelatin,starch, polyvinyl alcohol, and carboxymethyl cellulose orwater-insoluble powder such as calcium carbonate and magnesium carbonateis added. Furthermore, the size of the particle of product polymerdiffers depending on the agitation speed. Also, the controlling of thetemperature is easy since the heat of polymerization created during thepolymerization is taken away by the surrounding solvent and thus thereis little localized heating. Industrially, the suspension polymerizationis widely adopted in making of polymers with high polymerization degreesuseful as moulding raw material to easily isolate the prepared polymer,such as polystyrene, polymethylmethacrylate, polyvinyl acetate, andpolyvinyl chloride. For the purpose of the present invention, morepreferable polymerization methods are solution polymerization,precipitation polymerization and bulk polymerization. It is possible touse, for example, a polymerization reaction wherein styrene is used notonly as the monomer but also as the solvent, or a bulk polymerizationwithout an addition of the solvent.

It is possible to conduct, as post-polymerization treatments,conventionally known procedures such as refining and separation andextraction. It is more preferable to program a further procedure such asa procedure wherein separation and filtration are effected with a helpof an organic solvent, a refining procedure wherein the solvent finingis effected with a help of a combination of a good solvent and a poorsolvent, and a procedure of reprecipitation.

As for the polymerization initiator which can be used on the occasion ofpolymerizing the afore-mentioned monomer, it is suitable to use aperoxide-containing polymerization initiator, an azo group-containingpolymerization initiator, a redox system initiator, and various others.It is also possible to effect the polymerization with heat (naturalpolymerization) without a use of a polymerization initiator.

Examples of the peroxide-containing polymerization initiator include:organic ones such as peroxy ester, peroxydicarbonate, dialkyl peroxide,peroxyketal, ketone peroxide, hydroperoxide, and diacyl peroxide;inorganic ones such as persulfate and hydrogen peroxide. Morespecifically, examples include: peroxy esters such as tert-butylperoxyacetate, tert-butyl peroxylaurate, tert-butyl peroxypivalate,tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutylate,tert-butyl peroxyneodecanoate, tert-hexyl peroxyacetate, tert-hexylperoxylaurate, tert-hexyl peroxypivalate, tert-hexylperoxy-2-ethylhexanoate, tert-hexyl peroxyisobutylate, tert-hexylperoxyneodecanoate, tert-butyl peroxybenzoate,α,α′-bis(neodecanoilperoxy)diisopropyl benzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutyl-peroxy-2-ethylhexanoate,1,1,3,3-tetramethylbutyl-peroxyneodecanoate,1-cyclohexyl-1-methylethyl-peroxyneodecanoate,2,5-dimethyl-2,5-bis(2-ethylhexanoilperoxy)hexane,1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxy isopropyl monocarbonate,tert-butyl-peroxy-2-ethylhexyloxy monocarbonate, tert-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis(benzoilperoxy)hexane, tert-butylperoxy-m-toluoylbenzoate, bis(tert-butylperoxy)isophthalate, tert-butylperoxy maleic acid, tert-butyl peroxy-3,5,5-trimethylhexanoate, and2,5-dimethyl-2,5-bis(m-toluoylperoxy)hexane; diacyl peroxides such asbenzoyl peroxide, lauroyl peroxide,2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, and isobutyryl peroxide;peroxydicarbonates such as diisopropylperoxydicarbonate, andbis(4-tert-butylcyclohexyl)peroxydicarbonate; peroxyketals such as1,1-di-tert-butylperoxy cyclohexane, 1,1-di-tert-hexylperoxycyclohexane, 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, and2,2-di-tert-butylperoxy butane; dialkyl peroxides such as di-tert-butylperoxide, dicumyl peroxide, and tert-butyl cumyl peroxide; and otherssuch as tert-butyl peroxy allyl monocarbonate.

Examples of azo group-containing polymerization initiator include2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis-isobutyronitrile,1,1′-azobis(cyclohexane-1-carbonitrile), and2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile).

Examples of the redox-type-initiator includes: a combination of apersulfate initiator such as potassium persulfate, sodium persulfate,and ammonium persulfate with a reductant such as meta sodium hydrogensulfite and sodium hydrogen sulfite; a combination of an organicperoxide with a tertiary amine, like combining benzoyl peroxide withdimethylaniline, or cumene hydroperoxide with an aniline; and acombination of an organic peroxide with a transition metal, likecombining cumene hydroperoxide with cobalt naphthate.

These polymerization initiators may be used singly or in combination oftwo or more if need be. The dosage of the polymerization initiator ispreferably 0.1-20 weight parts against 100 weight parts of the monomer,and more preferably 1-10 weight parts thereagainst.

Examples of the solvent useful for the polymerization reaction include:ketones such as acetone, methyl ethyl ketone, and methyl isobutylketone; esters such as ethyl acetate, butyl acetate, ethyl propionate,and cellosolve acetate; hydrocarbons such as hexane, octane, petroleumether, cyclohexane, styrene, toluene, and xylene; halogenatedhydrocarbons such as trichloroethylene, dichloromethane, and chloroform;ethers such as ethyl ether, dimethyl glycol, trioxane, andtetrahydrofuran; acetals such as methylal, and diethyl acetal; etheralcohols such as methyl cellosolve, ethyl cellosolve, isopropylcellosolve, butyl cellosolve, diethylene glycol, and monobutyl ether;aprotic polar solvents such as N,N-dimethylformamide,N,N-dimethylacetoamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide;and sulfur-containing and/or nitrogen-containing organic compounds suchas nitropropene and nitrobenzene; and these can be used singly or incombination of two or more.

Tables 20 through 26 show specific examples of the polymerizationreactions in which the reaction system consists of the styrenederivative represented by the Formula (3) or (6), monomers α, β, γ,which are different vinyl-group containing monomers, the polymerizationinitiator, and the solvent. The scope of the present invention is notlimited by these examples.

TABLE 20 Polymeri- Styrene Monomer α Oligomer β Oligomer γPolymerization Initiator Solvent zation Derivative (Chemical Name)(Chemical Name) (Chemical Name) (Chemical Name) (Chemical Name) Examples(wt. parts) (wt. parts) (wt. parts) (wt. parts) (wt. parts) (wt. parts)1 a1-1 Styrene — — t-Butyl peroxy DMF isopropyl- (9) (60) (—) (—) (5)(100) 2 a1-2 α-Methylstyrene — — t-Butyl peroxy isopropyl- Toluenemonocarbonate (9) (60) (—) (—) (4)  (80) 3 a1-1 Styrene Acrylic acid —t-Butyl peroxy isopropyl- DMF monocarbonate (4) (89)  (9) (—) (3) (300)4 b1-1 2,4-Dimethylstyrene Hydroxyethyl- — t-Hexyl peroxy pivalate THFacrylate (10)  (82) (10) (—) (6) (150) 5 b1-2 3,4-Diethyl- Isobutylmaleate 2-Ethylhexyl- t-Butyl peroxy pivalate Chloroform α-methylstyreneacrylate (14)  (75) (12) (10) (8) (300) 6 c1-1 4-Propyl- N,N-Diethyl-Hydroxypropyl- 1,1-Di(t-butylperoxy)- 1,4-Dioxane α-methylstyrenemethacrylamide acrylate cyclohexane (15)  (75)  (8)  (7) (9) (350) 7c1-2 3,4-Dimethyl- — — 2,2′-Azobis-4-methoxy- Dichloro- α-methylstyrene2,4-dimethyl methane valeronitrile (8) (96) (—) (—) (5) (250) 8 a2-12-methoxystyrene Diacetone- — t-Butyl peroxy- Propanol methacrylamide2-ethylhexanoate (6) (70) (16) (—) (7) (400) 9 a2-2 3-Propyl-Methacrylic acid — 2,5-Dimethyl-2,5-bis- Ethyl- α-methylstyrene(2-Ethylhexanoilperoxy) acetate hexane (6) (82) (15) (—) (3) (150) 10b2-1 4-Ethylstyrene Acrylonitrile 2-Ethylhexyl- t-Butyl peroxy-Diethylene- acrylate 2-ethylhexyl- glycol monocarbonate (15)  (90) (10)(15) (8) (200) 11 b2-2 2-Chlorostyrene N,N-Dimethylamino- Methacrylicacid t-Butyl peroxy- Isopropyl- propylacrylamide maleic acid cellosolve(8) (70)  (7) (10) (3) (200) 12 c2-1 2,5-Dimethyl- 2-Hydroxypropyl- —2,5-Dimethyl-2,5-di- Diethylene- α-methylstyrene methacrylate(t-butylperoxy)hexyne-3 glycol (3) (81) (20) (—) (5) (300)

TABLE 21 Polymeri- Styrene Monomer α Oligomer β Oligomer γPolymerization Initiator Solvent zation Derivative (Chemical Name)(Chemical Name) (Chemical Name) (Chemical Name) (Chemical Name) Examples(wt. parts) (wt. parts) (wt. parts) (wt. parts) (wt. parts) (wt. parts)13 c2-2 3-Chloro- Hydroxypropyl- Isobutyl maleate 1,1-Di-(t-hexylperoxy)N-Methyl-2- α-methylstyrene acrylate cyclohexane pyrrolidone (12) (60)(15) (16) (6) (250) 14 d1-1 2,3-Diethylstyrene Itaconic acidN,N-Diethylmeth- t-Butyl peroxyacetate Octane acrylamide (30) (50) (20)(20) (4) (400) 15 d1-3 α-Methylstyrene — — 2,2′-Azobis- Benzene(2,4-dimethylvaleronitrile) (20) (60) (—) (—) (7) (200) 16 e1-2 StyreneMonobutyl- Methacrylamide t-Butyl peroxybenzoate Methyl- maleatecellosolve  (5) (70)  (8)  (6) (3) (300) 17 e1-7 2,3-DiethylstyreneMethacrylamide — 2,2′-Azobisisobutyronitrile Toluene (11) (76) (15) (—)(7) (150) 18 d2-1 2-Ethyl-3-Methyl- Acrylamide 2-Hydroxypropyl-1,1,3,3-Tetramethylbutyl- DMF α-methylstyrene methacrylateperoxy-2-ethylhexanoate  (8) (75) (20) (10) (4) (150) 19 d2-2 3-Ethyl-n-Butyl acrylate — Bis(4-t-butylcyclohexyl)- THF α-methylstyreneperoxydicarbonate  (3) (82) (15) (—) (5) (200) 20 e2-12,4-Diethylstyrene 2-Ethylhexyl- Acryloyl- Bis(4-t-butylcyclohexyl)-Methyl- acrylate morpholine peroxydicarbonate ethyl- ketone (14) (71) (5) (10) (7) (200) 21 e2-5 3-Methyl- — — Diisopropylperoxy- Dimethyl-α-methylstyrene dicarbonate glycol (17) (60) (—) (—) (5) (300)

TABLE 22 Polymeri- Styrene Monomer α Oligomer β Oligomer γPolymerization Initiator Solvent zation Derivative (Chemical Name)(Chemical Name) (Chemical Name) (Chemical Name) (Chemical Name) Examples(wt. parts) (wt. parts) (wt. parts) (wt. parts) (wt. parts) (wt. parts)22  e2-16 2,4-Diethylstyrene Acrylic acid Diacetone- t-Butyl peroxyisopropyl- N-Methyl-2- methacrylamide monocarbonate pyrrolidone (12)(65) (10) (15) (7) (300) 23 f1-1 Styrene — — t-Butyl peroxy isopropyl-DMF monocarbonate (15) (80) (—) (—) (4) (150) 24 f1-3 α-MethylstyreneMethacrylic acid — 2,5-Dimethyl-2,5-di- Diethylene-(t-butylperoxy)hexyne-3 glycol (12) (87) (10) (—) (10)  (300) 25 f2-12,4-Dimethylstyrene Acrylamide Acrylonitrile 2,5-Dimethyl-2,5-bis-Methyl- (2-ethylhexanoilperoxy)- acetate hexane  (3) (85) (10)  (9) (5)(150) 26 f2-4 2-Ethyl-3-methyl- Acrylic acid — 2,2′-Azobis-4-methoxy-Dichloro- α-methylstyrene 2,4-dimethyl valeronitrile methane (16) (75)(12) (—) (8) (250) 27 a1-1 Styrene — — — —  (2) (98) (—) (—) (—) (—) 28a1-1 Styrene — — t-Butyl peroxy isopropyl- — monocarbonate  (2) (98) (—)(—) (4) (—) 29 a3-2 Styrene — — t-Butyl peroxy isopropyl- Toluenemonocarbonate  (5) (80) (—) (—) (5)  (70) 30 a3-1 α-MethylstyreneAcrylic acid — t-Butyl peroxybenzoate THF (10) (60) (15) (—) (5) (230)

TABLE 23 Polymeri- Styrene Monomer α Oligomer β Oligomer γPolymerization Initiator Solvent zation Derivative (Chemical Name)(Chemical Name) (Chemical Name) (Chemical Name) (Chemical Name) Examples(wt. parts) (wt. parts) (wt. parts) (wt. parts) (wt. parts) (wt. parts)31 b3-3  Styrene — — t-Butyl peroxy isopropyl- DMF monocarbonate (15)(80) (—) (—) (4) (150) 32 b3-10 α-Methylstyrene Methacrylic acid —2,5-Dimethyl-2,5-di- Diethylene- (t-butylperoxy)hexyne-3 glycol (12)(87) (10  (—) (10)  (300) 33 c3-2 3-Methyl- — — Diisopropylperoxy-Dimethyl- α-methylstyrene dicarbonate glycol (17) (60) (—) (—) (5) (300)34 b1-23 Styrene — — t-Butyl peroxy isopropyl- Toluene monocarbonate (5) (80) (—) (—) (5)  (70) 35 a1-26 α-Methylstyrene Acrylic acid —t-Butyl peroxybenzoate THF (10) (60) (15) (—) (5) (230) 36 A2-22 Methacrylic acid Acrylamide — 1,1,3,3-Tetramethylbutyl- Dichloro-peroxy-2-ethylhexanoate methane  (8) (70) (15) (—) (7) (300) 37 a3-242,3-Diethylstyrene — — 2,5-Dimethyl-2,5-di- DMF (t-butylperoxy)hexyne-3(10) (90) (—) (—) (6) (250) 38 b1-26 2-Chlorostyrene AcrylonitrileMethacrylamide t-Butyl peroxy maleic acid Diethylene- glycol  (5) (81)(10) (5) (6) (350) 39 b2-18 2,4-Diethylstyrene Acrylamide Acrylonitrile2,5-Dimethyl-2,5-bis- Diethylene- (2-ethylhexanoilperoxy)- glycol hexane (7) (82)  (6) (9) (5) (350) 40 b3-18 3-Methyl- — — Diisopropylperoxy-Dimethyl- α-methylstyrene dicarbonate glycol (12) (83) (—) (—) (5) (300)

TABLE 24 Polymeri- Styrene Monomer α Oligomer β Oligomer γPolymerization Initiator Solvent zation Derivative (Chemical Name)(Chemical Name) (Chemical Name) (Chemical Name) (Chemical Name) Examples(wt. parts) (wt. parts) (wt. parts) (wt. parts) (wt. parts) (wt. parts)41  c1-28 Styrene Monobutyl maleate Methacrylamide t-Butylperoxybenzoate Methyl- cellosolve (2) (84)  (8)  (7) (3) (300) 42  c2-213-Propyl- Methacrylic acid — 2,5-Dimethyl-2,5-bis- Ethyl-α-methylstyrene (2-ethylhexanoilperoxy)- acetate hexane (3) (70) (15)(—) (3) (150) 43  d2-17 α-methylstyrene — — t-Butyl peroxy Tolueneisopropyl- monocarbonate (9) (74) (—) (—) (4) (230) 44  e1-19 4-Propyl-N,N-Diethyl- Hydroxypropyl- 1,1-Di(t-butylperoxy)- 1,4-Dioxaneα-methylstyrene methacrylamide acrylate cyclohexane (10)  (70) (10)  (9)(9) (350) 45  f1-13 3-Chloro- Hydroxypropyl- Isobutyl maleate1,1-Di(t-hexylperoxy)- N-Methyl-2- α-methylstyrene acrylate cyclohexanepyrrolidone (12)  (57) (10) (15) (6) (250) 46 a1-2 Styrene — — t-Butylperoxy Toluene (5) isopropyl- a2-2 monocarbonate (5) (60) (—) (—) (4) (35) 47 b1-1 Styrene — — t-Butyl peroxy Toluene (3) isopropyl- b3-2monocarbonate (3) (60) (—) (—) (4)  (35) 48 c1-2 2,4-DiethylstyreneAcrylic acid Diacetone- t-Butyl peroxy N-Methyl-2- (4) methacrylamideisopropyl- pyrrolidone c2-2 monocarbonate (5) (65) (10) (15) (7) (300)49 d1-1 2,5-Dimethyl- 2-Hydroxypropyl- — 2,5-Dimethyl-2,5-di-Diethylene- (6) α-methylstyrene methacrylate (t-butylperoxy)hexane-3glycol d2-1 (1) (81) (20) (—) (5) (300) 50 e1-2 2,3-DiethylstyreneItaconic acid N,N-Diethyl- t-Butylperoxy acetate Octane (8)methacrylamide d3-2 (1) (50) (20) (20) (4) (400)

TABLE 25 Polymeri- Styrene Monomer α Oligomer β Oligomer γPolymerization Initiator Solvent zation Derivative (Chemical Name)(Chemical Name) (Chemical Name) (Chemical Name) (Chemical Name) Examples(wt. parts) (wt. parts) (wt. parts) (wt. parts) (wt. parts) (wt. parts)51 f1-1 3,4-dimethyl- — — 2,2′-Azobis-4-methoxy- Dichloro- (5)α-methylstyrene 2,4-dimethyl valeronitrile methane f2-1 (3) (96) (—) (—)(5) (250) 52 a1-2 4-propyl- N,N-Diethyl(meth)- Hydroxypropyl-1,1-Di(t-butylperoxy)- 1,4-Dioxane (3) α-methylstyrene acrylamideacrylate cyclohexane d1-1 (3) (75)  (8) (7) (9) (350) 53 b3-22-Chlorostyrene N,N-Dimethyl- Methacrylic acid t-Butyl peroxy maleicacid Isopropyl- (7) aminopropyl- cellosolve e1-2 acrylamide (3) (70) (7) (10)  (3) (200) 54 f1-1 2,4-Dimethylstyrene AcrylamideAcrylonitrile 2,5-Dimethyl-2,5-bis- Ethyl- (3) (2-ethylhexanoilperoxy)-acetate d1-1 hexane (3) (85) (10) (9) (5) (150) 55 a2-1 α-MethylstyreneMethacrylic acid — 2,5-Dimethyl-2,5-di- Diethylene- (3)(t-butylperoxy)hexyne-3 glycol d2-1 (4) (87) (10) (—) (10)  (300)

TABLE 26 Polymeri- Styrene Monomer α Oligomer β Oligomer γPolymerization Initiator Solvent zation Derivative (Chemical Name)(Chemical Name) (Chemical Name) (Chemical Name) (Chemical Name) Examples(wt. parts) (wt. parts) (wt. parts) (wt. parts) (wt. parts) (wt. parts)56 a1-2 Styrene Monobutyl maleate Methacrylamide t-Butyl- Methyl- (5)peroxybenzoate cellosolve a2-1 (3) b3-2 (7) (84)  (8) (7) (3) (300) 57b1-3 4-Propyl- N,N-Diethyl- Hydroxypropyl- 1,1-Di(t-butylperoxy)-1,4-Dioxane (3) α-methylstyrene methacrylamide acrylate cyclohexane e3-1(1) f2-3 (5) (70) (10) (9) (9) (350) 58 e2-1 2,3-Diethylstyrene — —2,5-Dimethyl-2,5-di- DMF (2) (t-butylperoxy)hexane-3 d3-5 (2) d1-3 (5)(90) (—) (—) (6) (250)

The styrene derivatives in Tables 20 through 26 are the same compoundsas those exemplified in Tables 1 through 18. Also in them, “tert-” isabridged to “t-”, “tetrahydrofuran” to “THF”, and“N,N-dimethylformamide” to “DMF”.

Method B, which is another method for making the charge control resin(styrene-based resin) of the present invention, includes at least a stepto obtain a polymer from vinylphenyl alkylene halide and other monomersand a step thereafter to react the thus obtained polymer with dihydroxyaromatic carboxylic acid or dihydroxy aromatic carboxylic acid alkylester to obtain the constituent unit represented by the Formula (1). Ina preferable method of this kind, vinylphenyl alkylene halide as thestarting monomer, which becomes the constituent unit represented by theFormula (1), is mixed with a polymerization initiator in a solvent, andthus the monomer is polymerized to obtain the polymer; thereafter, areaction is conducted involving a dihydroxy aromatic carboxylic acid ora dihydroxy aromatic carboxylic acid alkyl ester to synthesize theconstituent unit represented by the Formula (1).

It is possible to use, as the vinylphenyl alkylene halide, any of thevinylphenyl alkylene halides exemplified with respect to Method A. Theother monomers that can be used in Method B include the vinylgroup-containing monomers previously exemplified with respect to MethodA. As specific examples of such reaction, wherein vinylphenyl alkylenehalide is copolymerized with vinyl aromatic hydrocarbon-containingmonomer represented by the Formula (4) to obtain a copolymer and then itis reacted with dihydroxy aromatic carboxylic acid derivative. It isexplained by following Reaction Formulae (12) and (13) for furtheranceof the explanation. However, the scope of the present invention shallnot be limited by these.

The first reaction in Method B derivatizes, in the first place, apolymer by polymerizing a vinylphenyl alkylene halide having a groupreactive to the dihydroxy aromatic carboxylic acid derivative withmonomer α, β or γ, which are monomers containing respectively differentvinyls, like in the case of the styrene monomer of the Formula (3)represented by the Reaction Formula (8). It is preferable to use apolymerization initiator in this polymerization reaction. In thefollowing Reaction Formula (12), the vinyl aromatichydrocarbon-containing monomer shown in the Formula (4) corresponds tothe monomer α. It is possible to conduct this polymerization by any ofthe known methods such as solution polymerization, suspensionpolymerization, emulsion polymerization, dispersion polymerization,precipitation polymerization, and bulk polymerization, and the inventionis not limited with regard to the method. As for the monomer,polymerization initiator, reaction solvent, reaction condition, etc. itis possible to use the same things as are exemplified with respect toMethod A.

In the Reaction Formula (12), X is a halogen atom such as F, Br and Cl,and R², R³, R⁴, R⁵ and g are the same as above.

The second reaction in Method B consists in synthesizing the constituentunit represented by the Formula (1), which is to be used in the presentinvention, by reacting the constituent unit in the polymer which hasbeen obtained in the first polymerization reaction, that is the polymerobtained from the vinylphenyl alkylene halide, with dihydroxy aromaticcarboxylic acid derivative. As for the dihydroxy aromatic carboxylicacid, it is possible to use the same things as are exemplified withrespect to Method A. Also, as for the reaction solvent, reactioncondition, etc., it is possible to use the same reaction conditiondescribed with regard to the synthesis of the styrene derivative inMethod A and the same reaction solvent described with regard to thesynthesis of the styrene derivative in Method A may be used. Thefollowing Reaction Formula (13) represents a case wherein the vinylaromatic hydrocarbon-containing monomer represented by the Formula (4)is used.

In the Reaction Formula (13), X, R¹, R², R³, R⁴, R⁵, g and h are thesame as above.

It is preferable that the charge control resin of the present inventionhas a glass transition temperature of 70-150° C. More preferably,80-130° C. If a toner or a high molecular compound for electrostaticcharge image developing containing this styrene-based resin is made bymolten kneading, it is possible to effectively increase theelectrification capacity by conducting the molten kneading at atemperature equal to or above the glass transition temperature, at whichthe fluidity of the charge control resin is increased, because thecompatibility of the charge control resin to the binder resin (forexample, resin for toner) is heightened and thus it becomes possible todisperse the charge control resin uniformly.

It is preferable that the number average molecular weight (Mn) of thecharge control resin falls in the range of 3000-50000 and the weightaverage molecular weight (Mw) falls in the range of 4000-500000; andfurther it is preferable that the value of Mw/Mn, which is obtained bydividing the weight average molecular weight (Mw) by the number averagemolecular weight (Mn) and is an indicator of molecular weightdistribution, is 1-25. Moreover, it is better that the number averagemolecular weight (Mn) is 5000 through 30000 and the weight averagemolecular weight (Mw) is 4000 through 300000, and that the molecularweight distribution ratio (Mw/Mn) is 1 through 15. When the value ofMw/Mn is close to 1.0, the situation is more monodisperse, and thecompatibility to the binder resin is higher. For this reason, it ispossible to disperse the charge control resin uniformly and thus theelectrification capacity is efficiently manifested.

It is preferable that the charge control resin generates heat and losesweight in a thermogravimetric differential thermal analysis (TG-DTA)measurement when the temperature is in a range of 200-450° C. It is morepreferable that the heat generation and the weight loss are observed ina range of 250-400° C. The temperature at which the heat generation andthe weight loss are simultaneously observed is the temperature at whichthe charge control resin undergoes decomposition by combustion, and itneed be equal to or higher than the temperature as of the time when thecharge control resin has been added to the binder resin and thermaldispersion process is taking place.

It is preferable that the volume resistive value of the charge controlresin is 0.1×10¹⁶−7.0×10¹⁷ Ωcm. The binder resin containing the chargecontrol resin would leak the electric charge it has acquired with timeif the volume resistive value is lower than this range, and on the otherhand if the volume resistive value is higher than this range, theelectric charge acquired becomes so much that the stability is lost. Itis more preferable if the volume resistive value is 0.5×10¹⁶−1.5×10¹⁷Ωcm, and even more preferable if 0.6×10¹⁶−0.5×10¹⁷ Ωcm. The binder resincontaining the charge control resin having such a volume resistive valueacquires a sufficient amount of electric charge and exhibits a goodcharging speed and good temporal stability. Incidentally, the volumespecific resistance is measured in accordance with JIS Standard (K6911).

The styrene derivative which makes the constituent unit of the polymerwhich is the active ingredient of the charge control resin of thepresent invention is also useful as the charge control agent besides itsusefulness as the monomer used for the charge control resin.

By giving the styrene derivative used in the present invention aconstituent part which gives rise to a good compatibility to the resinused in this application, it is possible to disperse it through theresin uniformly at a molecular level. In this manner, it is possible toexert the styrene derivative's charging characteristics to the utmostwith the minimum dosage thereof. Furthermore, by using a styrene-basedresin having a polymer which has a styrene derivative as its monomer anda copolymer of such polymer, it is possible, in applications wherein aresin having a similar or analogous composition is used, to improve thecompatibility to the resin and thus to effect a uniform dispersion toobtain a good composition.

Therefore, used as the charge control agent, the substance of thepresent invention can exert the charging characteristics to far higherdegrees compared to the conventional charge control agents. Also, thecharge controllability is stable and the fastness is improved.

As a charge control agent, the styrene derivative (charge control agent)and the charge control resin (styrene-based resin) are supposed to becontained in a toner or powdery paint or the like for electrostaticcharge image developing. It is preferable that the dosage of the styrenederivative (charge control monomer) or the charge control resin is 0.1to 10 weight parts against 100 weight parts of the resin used.Furthermore, it is more preferable that the dosage of the styrenederivative (charge control monomer) or the charge control resin is 0.5to 7 weight parts against 100 weight parts of the resin used.

It is possible to exemplify the following known resins to go with toner(binder resins) as the examples of resin for toner applicable to thepresent invention. Namely, thermoplastic resins such as styrene resin,styrene-acrylic resin, styrene-butadiene resin, styrene-maleic acidresin, styrene-vinylmethylether resin, styrene-methacrylic acid estercopolymer, polyester resin, and polypropylene resin can be exemplified.These resins can be used singly or in a blend of two or more.

Incidentally, it is possible to use the styrene derivative (chargecontrol agent) and charge control resin used in the present inventionfor the purpose of controlling (intensifying) the chargeability of astatic powdery paint by dosing it in the resin powder. In this case,examples for the resin for the paint include thermoplastic resins suchas acrylic resins, polyolefin-containing resins, polyester-containingresins, and polyamide-containing resins and thermosetting resins such asphenol-containing resins, epoxy-containing resins, polyester-containingresin; and these can be used singly or in a mixture of two or more.

As the colorant for the toner, it is possible to use various dyes andpigments singly or in a blend of two or more. Examples of acceptable thecolorant include organic pigments such as monoazo yellow, disazo yellow,azomethine yellow, quinophthalon yellow, quinoline yellow, isoindolinoneyellow, perinone orange, perinone red, perylene maroon, rhodamine 6Glake, quinacridone red, anthrone red, rose bengal, copper phthalocyanineblue, copper phthalocyanine green, and diketo pyrrolo pyrrole-containingpigment; inorganic pigments and metal powders such as carbon black,titanium white, titanium yellow, ultramarine, cobalt blue, red ochre,aluminum powder, and bronze; various oil soluble dyestuff and dispersedyes such as azo dye, quinophthalone-containing dye,anthraquinone-containing dye, phthalocyanine-containing dye,indophenol-containing dye, and indoaniline-containing dye; andtriarylmethane-containing dyes and xanthene-containing dyes such asrosin, rosin modified phenol and rosin modified maleic acid which aremodified by resin. These can be used singly or in a mixture of two ormore.

The toner can be made by using any of generally known methods. Forexample, a method for manufacturing a toner for electrostatic imagedevelopment employs a mixer such as ball mill to mix together thoroughlya resin for toner, a pigment, and the styrene derivative (charge controlagent) and/or charge control resin of the present invention, and, ifneed be, a magnetic material (for example, fine powder made of strongmagnetic substance such as iron, cobalt and ferrite), a fluiditymodifier (such as silica, aluminum oxide and titanium oxide), an offsetinhibitor (such as wax and low molecular weight olefin wax), adispersion stabilizer, and a light stabilizer. Thereafter, the mixtureis melt and blended by means of a thermal kneading machine such as aheating roll, kneader, and extruder. Then, the mixture is cooled andsolidified, and the solidified mixture is crushed and classified, andthen a toner of a desired average particle size, such as 1-20micrometers, is obtained.

It is possible to provide the styrene derivative (charge control agent)or charge control resin used in the present invention as an enhancer forcharge controlling or enhancement, or as a powdery paint forelectrostatic painting containing the enhancer and resin. They maycontain one kind of the enhancer or may contain more kinds. A preferabledosage of the enhancer is 0.1 to 10 weight parts against 100 weightparts of the resin, or more preferably 0.5 to 5 weight parts against 100weight parts of the resin. The resin and the pigment useful in thepowdery paint for electrostatic painting can be exemplified by the onesmentioned above with regard to the toner.

Such powdery paint for the electrostatic painting is excellent inenvironmental resistance and durability, and by virtue of the powderypaint the coating efficiency becomes nearly 100% and the coatingperformance is improved, and it is possible to form a thick film free offilm defect. As the enhancer is either colorless or pale-colored, colortone noise is hard to occur in the paint film.

This powdery paint for electrostatic painting may be manufactured bymeans of any of generally known manufacturing methods. For example, amethod for manufacturing a powdery paint for electrostatic paintingemploys a mixer such as ball mill to mix together uniformly the addedsubstances such as the charge enhancer and resin of the presentinvention, and, depending on the application and purpose, a pigment, afluidity modifier, a powdery paint for electrostatic painting, filler,hardener, and plasticizer. Thereafter, the mixture is melt and blendedby means of a thermal kneading machine such as a heating roll, kneader,and extruder. Then, the mixture is cooled and solidified, and crushedand classified, and then a powdery paint for electrostatic paintinghaving a desired particle size, such as 10-250 micrometers, is obtained.

It is possible to conduct the painting of this powdery paint forelectrostatic painting by means of any of generally employedelectrostatic painting methods such as corona application method,frictional electrification method, and hybrid method.

EMBODIMENTS

Embodiments of the present invention are detailed more, but the presentinvention is not limited by these embodiments.

Examples of synthesis of the styrene derivative for derivation towardthe charge control resin of the present invention are shown in ExamplesA1 through A15.

Example A1

100.0 g of 2,5-dihydroxy benzoic acid was dissolved by being stirred in2 liters of methanol, and this was added with 88.3 g of potassiumcarbonate and heated to 67° C. Into this reaction liquid was dripped102.0 g of 4-(chloromethyl)styrene in the course of 22 minutes, and areaction was allowed to proceed for 12 hours at 67° C. This reactionliquid was cooled, and methanol was removed by distillation under areduced pressure and was cleansed with hexane and was filtrated. Theresidue was dissolved in methanol and was reprecipitated by beingdripped in water and the precipitate was filtered aside. Thisreprecipitation procedure was repeated twice, and the final residue wasdried at 80° C. for 48 hours, and 48.7 g of styrene derivative (CompoundExample a1-1) represented by the following Formula (A1) was obtained.

Thus obtained styrene derivative (A1) was examined by high-performanceliquid chromatography (HPLC: Detector SPD-M20A manufactured by ShimadzuCorporation; column oven: CTO-20A; pump: LC-20AT; degasser: DGU-20A₃)under the following conditions and its purity was confirmed to be 94.6%.

HPLC measurement conditions: 3 mg of the sample was dissolved in 10 mlof tetrahydrofuran (THF), to which then ultrasonic wave was applied for30 minutes, and by filtration with a solvent-resistant membrane filterhaving a pore diameter of 0.5 micrometer a sample solution was obtained,and it was investigated under the following conditions.Column: L-Column ODS (4.6×250 mm); column oven temperature: 40° C.Flow velocity: 1.0 ml/minute; sample dosage: 3 microliters; detectionwave length: 254 nm.Elute-(1): THF:0.05 M-CH₃COONH₄ aqueous solution=4:6Elute-(2): THF:0.05 M-CH₃COONH₄ aqueous solution=6:4Elute-(1): Elute-(2)=100:0 then (20 minutes) then 0:100

The obtained styrene derivative (A1) was examined by means of ¹H-nuclearmagnetic resonance apparatus (NMR: FT-NMR JNM-AL 300 manufactured byJEOL Ltd.) under conditions where the resonance frequency was 300 MHz,the measurement nuclide was ¹H, the used solvent was heavy DMSO, and themeasurement temperature was room temperature. ¹H-NMR spectral data wereas follows, and are supportive of the structure represented by theFormula (A1). The results of the measurement by ¹H-NMR are shown in FIG.1.

δ(ppm)=5.06 (2H, s, —CH₂—), 5.27 (1H, d, C—H), 5.84 (1H, d, C—H), 6.74(1H, d-d, —CH═), 6.91 (1H, d, Ar—H), 7.23 (1H, d-d, Ar—H), 7.35 (1H, d,Ar—H), 7.41 (1H, d, Ar—H), 7.49 (2H, d, Ar—H).

In the ¹H-NMR, irradiation was conducted upon the proton of 5.06 ppm(2H, s, —OCH₂—), a nuclear Overhauser effect (NOE) of 16.9% was observedat the aromatic proton of 7.35 (1H, d, Ar—H). The measurement result ofthis NOE is shown in FIG. 2.

With regard to the obtained styrene derivative (A1), the weight ratioamong carbon (C), hydrogen (H) and nitrogen (N) was measured by anelemental analyzer (totally automatic elemental analyzer 2400II forCHNS/O analysis manufactured by PerkinElmer Corp.). The theoreticalvalues and the measured values by the elemental analysis are givenbelow.

Measured values: C, 71.61; H, 4.90; N, 0.00

Theoretical values: C, 71.10; H, 5.22; N, 0.00

With regard to the obtained styrene derivative (A1), a measurement byKBr method was conducted with a Fourier transform infraredspectrophotometer (FT-IR; JIR-SPX60S manufactured by JEOL Ltd.), and themeasurement result was as follows:

v(cm⁻¹)=3132, 3088, 2924, 2877, 1680, 1614, 1593, 1516, 1487, 1471,1443, 1408, 1379, 1250, 1196, 1011, 906, 860, 831, 808, 789, 775, 744,715, 675, 559, 492, 472.

The measurement result by FT-IR is shown in FIG. 3.

With regard to the obtained styrene derivative (A1), a measurement wasconducted by a differential thermal/thermogravimetry simultaneousanalyzer (TG-DTA6200 EXSTAR6000 manufactured by SII Nanotechnology Inc.)under a condition whereby temperature was raised from 30° C. to 550° C.,at a rate of 10° C./minute. The measurement result of the simultaneousthermogravimetric and differential thermal analysis (TG-DTA) is as shownin FIG. 4. It was observed by the measurement that the melting point was168° C., the heat generation temperature was 551° C., and the weightloss temperatures were 210° C., 404° C. and 521° C.

With regard to the obtained styrene derivative (A1), a measurement wasconducted with a liquid chromatography/mass spectrometry analyzer(LC/3DQMS System M-8000 manufactured by Hitachi High-Technologies Corp.)under the following conditions.

LC/MC measurement conditions were as follows:

Ionized source: ESI ionized source (measured by FI method)

Carrier: methanol for industrial electronics;

Sample preparation method: 1 mg each of the samples was dissolved in themethanol for industrial electronics. In cases of samples which did notdissolve completely, tetrahydrofuran was added to complete thedissolution.

First pore temperature: 120° C.;

Second pore temperature: 100° C.;

Desolventizing temperature: 150° C.;

Auxiliary gas temperature: 150° C.;

Focus voltage: 20 V;

Drift voltage: 20 V;

The result of the liquid chromatography/mass spectrometry analysis isshown in FIG. 5. Also, the theoretical values and the measured values bythe mass spectrometry were as shown below:

measured values: LC/MS m/z=269.00 [M-H]⁻

theoretical values: m/z=270.09

Example A2

100 g of 2,5-dihydroxy benzoic acid and 1441 g of 80% sulfuric acid weremixed and heated at a temperature of 50° C., and 144 g of tert-butanolwas added to this dispersion, which was stirred for 30 minutes at atemperature of 50° C. Thereafter, this process of adding 144 g oftert-butanol to the dispersion followed by 30 minutes stirring wasrepeated for three times. The reaction solution was cooled to the roomtemperature, and was gradually poured into 1 kg of ice water, and thedeposit was filtered aside, and washed with water and then with hexane.The resultant deposit was dissolved in 200 ml of methanol, and wasreprecipitated in 3.6 liters of water. After filtration, the resultantdeposit was dried for 24 hours at 80° C., and 74.9 g of tert-butylatedsalicylic acid intermediate was obtained.

25.0 g of the thus obtained salicylic acid intermediate was dissolved in150 ml of methanol while being stirred, and 36.9 g of potassiumcarbonate was added and heating was conducted at 65° C. A solutionobtained by dissolving 18.7 g of 4-(chloromethyl) styrene in 100 ml ofmethanol was dripped into this reaction liquid, and reaction was allowedto proceed for 3 hours at 65° C. This reaction liquid was cooled,filtrated, and the methanol in the filtrate was removed by distillationunder a reduced pressure and a deposit was obtained.

The obtained deposit was dispersed in 1.5 liters of water of pH 2, andethyl acetate was added and thereby an extraction was conducted.Thereafter, the solution was separated and added with water with whichit was washed, and after the ethyl acetate layer was separated, it wasdried with magnesium sulfate, and the ethyl acetate was removed bydistillation under a reduced pressure, and a deposit was obtained. Theobtained deposit was washed with hexane and was filtrated aside. Thedeposit was recrystallized by using a mixed solution of toluene andethyl acetate. This was dried at 80° C. for 40 hours, and 20.1 g ofstyrene derivative (Compound Example a1-2) represented by the followingFormula (A2) was obtained.

The thus obtained styrene derivative (A2) was examined for HPLC purityunder conditions described in Example A1, and it was 98.6%.

¹H-NMR measurement was conducted on the obtained styrene derivative (A2)in the same manner as described in Example A1 except that CDCl₃ was usedas the measurement solvent. ¹H-NMR spectrography data were as follows,and are supportive of the structure represented by the Formula (A2).FIG. 6 shows the measurement result of ¹H-NMR.

δ(ppm)=1.41 (9H, s, —C(CH₃)₃), 5.00 (2H, s, —OCH₂—), 5.26 (1H, d, C—H),5.76 (1H, d, C—H), 6.73 (1H, d-d, —CH═), 7.25 (1H, d, Ar—H), 7.31 (1H,d, Ar—H), 7.40 (1H, d, 7.44 (1H, d, Ar—H)

In the foregoing ¹H-NMR, when the proton of 5.00 (2H, s, —OCH₂—) wasirradiated at, a 8.1-% nuclear Overhauser effect was observed at thearomatic proton of 7.25 (1H, d, Ar—H).

The obtained styrene derivative (A2) was measured for FT-IR under thesame conditions as Example A1, and the following was observed.

v(cm⁻¹)=3419, 3093, 3005, 2964, 2866, 2710, 2619, 1894, 1819, 1788,1774, 1753, 1660, 1630, 1608, 1570, 1514, 1483, 1470, 1429, 1406, 1394,1373, 1362, 1331, 1290, 1277, 1225, 1200, 1180, 1117, 1066, 1016, 985,970, 958, 908, 889, 850, 833, 818, 806, 795, 721, 681, 658, 606, 528,515, 494, 465, 428, 420.

FIG. 7 shows the result of the measurement conducted on the obtainedstyrene derivative (A2) for TG-DTA under the same conditions describedin Example A1. It was observed by the measurement that the melting pointwas 183° C., the heat generation temperatures were 517° C. and 563° C.,the weight loss temperatures were 161° C., 386° C., 489° C. and 553° C.

Elementary analysis was conducted on the obtained styrene derivative(A2) under the same conditions as described in Example A1. Thetheoretical values and the measured values by the elemental analysis aregiven below.

measured values: C, 74.29; H, 6.71; N, 0.00.

theoretical values: C, 73.60; H, 6.79; N, 0.00.

On the obtained styrene derivative (A2) was conducted liquidchromatography/mass spectrometry analysis using the same conditions asdescribed in Example A1. The theoretical values and the measured valuesby the mass spectrometry are given below.

measured values: LC/MC m/z=324.86 [M-H]⁻

theoretical values: m/z=326.15

Example A3

78.63 g of 2,4-dihydroxy benzoic acid was dissolved in 400 ml ofmethanol with stirring, and 152.03 g of potassium carbonate was addedand heated at a temperature of 60° C. A solution consisting of a mixtureof 87.88 g of 4-(chloromethyl)styrene and 100 ml of methanol was drippedinto the reaction liquid, and a reaction was allowed to proceed for 2.5hours at 60° C. The resultant reaction solution was cooled, and thedeposit was separated by filtration and washed with methanol.

The residue was dispersed by chloric acid in one liter of water of pH 1.Thereafter, it was filtered aside and washed with water and dried at 80°C., and 55.71 g of white styrene derivative (Compound Example b1-1)represented by the following Formula (A3) was obtained.

The thus obtained styrene derivative (A3) was examined under the sameconditions as described in Example A1 and the HPLC purity was found tobe 97.7%.

With respect to the obtained styrene derivative (A3), ¹H-NMR wasconducted under the same conditions as described in Example A1. ¹H-NMRspectral data were as described below and are supportive of the Formula(A3).

δ(ppm)=5.09 (2H, s, —CH₂—), 5.27 (1H, d, C—H), 5.85 (1H, d, C—H),6.38-6.41 (2H, m, Ar—H), 6.74 (1H, d-d, C═H), 7.41 (2H, d, Ar—H), 7.49(2H, d, Ar—H), 7.61 (1H, d, Ar—H)

In the foregoing ¹H-NMR, when the proton of 5.09 (2H, s, —OCH₂—) wasirradiated at, a 17.2-% nuclear Overhauser effect was observed at thearomatic proton of 6.38-6.41 (2H, m, Ar—H).

The obtained styrene derivative (A3) was measured for FT-IR under thesame conditions as Example A1, and the following was observed.

v(cm⁻¹)=3086, 3005, 1639, 1589, 1514, 1502, 1450, 1379, 1288, 1254,1182, 1157, 1105, 1095, 1014, 904, 827, 779, 729, 698, 649, 596, 532,471.

A measurement was conducted on the obtained styrene derivative (A3) forTG-DTA under the same conditions described in Example A1, and it wasobserved by the measurement that the melting point was 184° C., the heatgeneration temperature was 571° C., the weight loss temperatures were216° C., 430° C. and 554° C.

Elementary analysis was conducted on the obtained styrene derivative(A3) under the same conditions as described in Example A1. Thetheoretical values and the measured values by the elemental analysis aregiven below.

measured values: C, 64.65; H, 4.23; N, 0.00.

theoretical values: C, 71.10; H, 5.22; N, 0.00.

On the obtained styrene derivative (A3) was conducted liquidchromatography/mass spectrometry analysis using the same conditions asdescribed in Example A1. The theoretical values and the measured valuesby the mass spectrometry are given below.

measured values: LC/MC m/z=269.07 [M-H]⁻

theoretical values: m/z=270.09

Example A4

25.0 g of 2,6-dihydroxy-4-methyl benzoic acid was dissolved in 450 ml ofmethanol with stirring, and 40.5 g of potassium carbonate was added andheated at a temperature of 65° C. A solution consisting of a mixture of23.4 g of 4-(chloromethyl)styrene and 100 ml of methanol was drippedinto the reaction liquid, and a reaction was allowed to proceed for 5hours at 65° C. The resultant reaction solution was cooled, and filteredand the methanol in the filtrate was removed by distillation under areduced pressure and a deposit was obtained.

The obtained deposit was dispersed in 1.5 liters of water of pH 2, andextraction was conducted by adding ethyl acetate. Thereafter, thesolution was separated and added with water for washing, and the ethylacetate layer was removed, and drying was conducted with magnesiumsulfate, and under a reduced pressure the ethyl acetate was distilledoff and a deposit was obtained. The obtained deposit was cleansed withhexane, and filtrated aside. The thus obtained deposit wasrecrystallized by means of a mixture solution of toluene and ethylacetate, and it was dried for 47 hours at 80° C., and 27.3 g of astyrene derivative represented by the following Formula (A4) wasobtained.

The thus obtained styrene derivative (A4) was examined for HPLC purityunder conditions described in Example A1, and it was 93.7%.

With respect to the obtained styrene derivative (A4), ¹H-NMR wasconducted under the same conditions as described in Example A1, exceptthat the measurement solvent used was CDCl₃. ¹H-NMR spectral data wereas given below and are supportive of the Formula (A4).

δ(ppm)=3.28 (3H, s, —CH₃), 4.39 (2H, s, —OCH₂—), 5.25 (1H, d, —C═C—H),5.83 (1H, d, —C═C—H), 6.73 (1H, d-d, —CH═), 7.17 (1H, d, Ar—H), 7.24(1H, d, Ar—H), 7.29 (1H, d, Ar—H), 7.45 (1H, d, Ar—H).

In the foregoing ¹H-NMR, when the proton of 4.39 ppm (2H, s, —OCH₂—) wasirradiated at, a 15.3-% nuclear Overhauser effect was observed at thearomatic proton of 7.29 (2H, d, Ar—H).

The obtained styrene derivative (A4) was measured for FT-IR under thesame conditions as Example A1, and the following was observed.

v(cm⁻¹)=3417, 3097, 3007, 2969, 2863, 2621, 1664, 1611, 1516, 1434,1371, 1333, 1295, 1279, 1228, 1202, 1114, 1064, 973, 911, 854, 836, 809,805, 724, 684, 496, 467.

A measurement was conducted on the obtained styrene derivative (A4) forTG-DTA under the same conditions described in Example A1, and it wasobserved by the measurement that the melting point was 156° C., the heatgeneration temperatures were 509° C. and 559° C., the weight losstemperatures were 163° C., 390° C., 476° C. and 549° C.

Elementary analysis was conducted on the obtained styrene derivative(A4) under the same conditions as described in Example A1. Thetheoretical values and the measured values by the elemental analysis aregiven below.

measured values: C, 69.93; H, 5.33; N, 0.00.

theoretical values: C, 71.82; H, 5.67; N, 0.00.

On the obtained styrene derivative (A4) was conducted liquidchromatography/mass spectrometry analysis using the same conditions asdescribed in Example A1. The theoretical values and the measured valuesby the mass spectrometry are given below.

measured values: LC/MC m/z=283.2 [M-H]⁻

theoretical values: m/z=284.1

Example A5

5.53 g of 5-tert-butyl-2,3-dihydroxy benzoic acid was dissolved in 30 mlof methanol with stirring, and 8.02 g of potassium carbonate was addedand heated at a temperature of 65° C. 4.12 g of 4-(chloromethyl)styrenewas dripped into this reaction liquid in the course of 15 minutes, and areaction was allowed to proceed for 3 hours at 65° C. The resultantreaction solution was cooled, and filtered. The methanol in the filtratewas removed by distillation under a reduced pressure and a deposit wasobtained. The obtained deposit was dispersed in water of pH 2, andextraction was conducted by adding ethyl acetate. Thereafter, thesolution was separated and added with water for washing, and the ethylacetate layer was removed, and drying was conducted with magnesiumsulfate, and under a reduced pressure the ethyl acetate was distilledoff. The resultant deposit was cleansed with toluene, and filtratedaside. The residue was dried for 40 hours at 80° C., and 4.55 g of astyrene derivative (Compound Example c1-2) represented by the followingFormula (A5) was obtained.

The thus obtained styrene derivative (A5) was examined under the sameconditions as described in Example A1 and the HPLC purity was found tobe 99.3%.

With respect to the obtained styrene derivative (A5), ¹H-NMR wasconducted under the same conditions as described in Example A1. ¹H-NMRspectral data were as given below and are supportive of the Formula(A5).

δ(ppm)=1.22 (9H, s, —C(CH_(,3))₃), 5.14 (2H, s, —CH₂—), 5.25 (1H, d,═C—H), 5.83 (1H, d, ═C—H), 6.73 (1H, d-d, ═C—H), 7.28 (1H, d, Ar—H),7.32 (1H, d, Ar—H), 7.43 (1H, d, Ar—H), 7.49 (1H, d, Ar—H)

In the foregoing ¹H-NMR, when the proton of 5.14 (2H, s, —CH₂—) wasirradiated at, an 8.5-% nuclear Overhauser effect was observed at thearomatic proton of 7.28 (114, d, Ar—H).

The obtained styrene derivative (A5) was measured for FT-IR under thesame conditions as Example A1, and the following was observed.

v(cm⁻¹)=3093, 3052, 2964, 2866, 2632, 1654, 1616, 1513, 1483, 1450,1406, 1304, 1277, 1238, 1198, 1120, 1080, 1016, 982, 958, 920, 893, 858,829, 818, 793, 710, 687, 644, 490

A measurement was conducted on the obtained styrene derivative (A5) forTG-DTA under the same conditions described in Example A1, and the resultis shown in FIG. 8. It was observed by the measurement that the meltingpoint was 142° C., the heat generation temperature was 592° C., and theweight loss temperatures were 201° C., 411° C. and 555° C.

Elementary analysis was conducted on the obtained styrene derivative(A5) under the same conditions as described in Example A1. Thetheoretical values and the measured values by the elemental analysis aregiven below.

measured values: C, 73.92; H, 6.64; N, 0.00.

theoretical values: C, 73.60; H, 6.79; N, 0.00.

On the obtained styrene derivative (A5) was conducted liquidchromatography/mass spectrometry analysis was conducted under the sameconditions as described in Example A1. The theoretical values and themeasured values by the mass spectrometry are given below.

measured values: LC/MC m/z=324.73 [M-H]⁻

theoretical values: m/z=326.15

Example A6

23.8 g of 5-bromo-2,4-dihydroxy benzoic acid was dissolved in 100 ml ofmethanol with stirring, and 30.4 g of potassium carbonate was added anddispersed and heated at a temperature of 62° C. for 30 minutes. 17.6 gof 4-chloromethylstyrene was dripped into the reaction liquid in thecourse of one hour, and a reaction was allowed to proceed under refluxfor 2.5 hours. After the reaction, the solution was cooled to the roomtemperature, and filtered. The obtained deposit was washed withmethanol, and then it was added to 300 ml of water and conditioned to pH1 with chloric acid, and dispersed for 30 minutes and filtered aside andwashed with water. The residue was dried at 80° C. for 48 hours, and13.5 g of white solid styrene derivative (Compound Example b1-21)represented by the following Formula (A6) was obtained.

The thus obtained styrene derivative (A6) was examined under the sameconditions as described in Example A1 and the HPLC purity was found tobe 96.7%.

With respect to the obtained styrene derivative (A6), ¹H-NMR wasconducted under the same conditions as described in Example A1. ¹H-NMRspectral data were as described below and are supportive of the Formula(A6).

δ(ppm)=5.27 (2H, s, —OCH₂—), 5.30 (1H, d, —C═C—H), 5.87 (1H, d, —C═C—H),6.75 (1H, d-d, —C═C—H), 6.79 (1H, s, Ar—H), 7.45 (2H, d, Ar—H), 7.53(2H, d, Ar—H), 7.90 (1H, s, Ar—H), 11.54 (1H, broad, OH)

In the foregoing ¹H-NMR, when the proton of 5.27 (2H, s, —OCH₂—) wasirradiated at, an 8.9-% nuclear Overhauser effect was observed at thearomatic proton of 6.79 (1H, s, Ar—H).

The obtained styrene derivative (A6) was measured for FT-IR under thesame conditions as Example A1, and the following was observed.

v(cm⁻¹)=3005, 2557, 1651, 1612, 1514, 1454, 1439, 1383, 1354, 1257,1192, 1117, 1049, 1016, 1005, 985, 904, 895, 842, 822, 787, 715, 683,606, 496, 455

A measurement was conducted on the obtained styrene derivative (A6) forTG-DTA under the same conditions described in Example A1, and it wasobserved by the measurement that the melting point was 232° C., the heatgeneration temperatures were 257° C. and 560° C., the weight losstemperatures were 227° C. and 510° C.

Elementary analysis was conducted on the obtained styrene derivative(A6) under the same conditions as described in Example A1. Thetheoretical values and the measured values by the elemental analysis aregiven below.

measured values: C, 55.35; H, 3.41; N, 0.00.

theoretical values: C, 55.04; H, 3.75; N, 0.00.

On the obtained obtained styrene derivative (A6) was conducted liquidchromatography/mass spectrometry analysis using the same conditions asdescribed in Example A1. The theoretical values and the measured valuesby the mass spectrometry are given below.

measured values: LC/MC m/z=348.80 [M-H]⁻

theoretical values: m/z=348.0

Example A7

201 g mixture of 2,5-dihydroxy benzoic acid and isopropanol was added to1201 g of 80% sulfuric acid and stirred for 8 hours at 75° C. Thesolution was allowed to cool, and was added with 2 liters of ice waterand 140 ml of hexane and was stirred in an ice bath. Resultant crystaldeposit was filtrated, and the residue was washed with hexane. Then, itwas dispersed in a mixture liquid consisting of methanol and water in aratio of 6:4, and filtration was conducted. The substance was dried for48 hours at 60° C., and 65.4 g of isopropyl-salicylic acid intermediatewas obtained.

22.5 g of isopropyl-salicylic acid intermediate was dissolved in 450 mlof methanol with stirring, and 60 g of potassium carbonate was added andheated at a temperature of 65° C. To this reaction liquid was added bydripping 96.8 g of 4-(2-chloroethyl)styrene, which had been synthesizedby the method described in Polymer Bulletin 19, 111-117 (1988) for threehours at 65° C. The resultant reaction solution was cooled and filtered.Then the methanol in the filtrate was removed by distillation under areduced pressure and a deposit was obtained. The obtained deposit wasdispersed in 1.5 liters of water of pH 2, and extraction was conductedby addition of ethyl acetate. Thereafter, the solution was separated andadded with water for washing, and the ethyl acetate layer was removed,and drying was conducted with magnesium sulfate, and under a reducedpressure the ethyl acetate was distilled off and a deposit was obtained.The obtained deposit was cleansed with hexane, and filtrated aside.

The thus obtained residue was recrystallized by means of a mixturesolution of toluene and ethyl acetate, and after a filtration, it wasdried for 44 hours at 80° C., and 26.3 g of a styrene derivative(Compound Example a1-20) represented by the following Formula (A7) wasobtained.

The thus obtained styrene derivative (A7) was examined for HPLC purityunder conditions described in Example A1, and it was found 96.6%.

With respect to the obtained styrene derivative (A7), ¹H-NMR wasconducted under the same conditions as described in Example A1. ¹H-NMRspectral data were as given below and are supportive of the Formula(A7).

δ(ppm)=1.24 (6H, d, —(CH₃)₂), 2.88 (1H, m, —CH—(CH₃)₂), 4.07 (2H, t,—O—CH₂—), 2.77 (2H, t, —O—CH₂—CH₂ —), 5.25 (1H, d, —C═C—H), (1H, d,—CH═CH), 6.73 (1H, d-d, —CH═CH₂ ), 6.94 (1H, d, Ar—H), 7.26 (1H, d,Ar—H), 7.32 (2H, d, Ar—H), 7.46 (2H, d, Ar—H)

In the foregoing ¹H-NMR, when the proton of 4.07 (2H, t, —O—CH₂—) wasirradiated at, a 9.1-% nuclear Overhauser effect was observed at thearomatic proton of 6.94 (1H, d, Ar—H).

The obtained styrene derivative (A7) was measured for FT-IR under thesame conditions as Example A1, and the following was observed.

v(cm⁻¹)=3431, 3018, 2878, 1679, 1620, 1455, 1345, 1236, 1132, 1236,1132, 1078, 930, 810, 740, 700, 506.

Elementary analysis was conducted on the obtained styrene derivative(A7) under the same conditions as described in Example A1. Thetheoretical values and the measured values by the elemental analysis aregiven below.

measured values: C, 75.60; H, 6.57; N, 0.00.

theoretical values: C, 73.60; H, 6.79; N, 0.00.

On the obtained styrene derivative (A7) was conducted liquidchromatography/mass spectrometry analysis using the same conditions asdescribed in Example A1. The theoretical values and the measured valuesby the mass spectrometry are given below.

measured values: LC/MC m/z=325.8 [M-H]⁻

theoretical values: m/z=326.1

Example A8

53.9 g of 2,3-dihydroxy benzoic acid was dissolved in 280 ml of methanolwith stirring, and 106 g of K₂CO₃ was added and heated at a temperatureof 65° C. and stirred for 30 minutes. 61.7 g of 4-chloromethylstyrenewas dripped into this reaction liquid in the course of one hour. Then, areaction was allowed to proceed under reflux for 3 hours. The reactionliquid was allowed to cool to the room temperature, and filtered; themethanol in the filtrate was removed under a reduced pressure, and abrown semi-solid was obtained. The obtained brown semi-solid wasdispersed in 2 liters of water of pH 1, and ethyl acetate was added andextraction was conducted. The ethyl acetate layer was washed with asaturate saline solution and the ethyl acetate layer was removed anddrying was conducted with magnesium sulfate, and the solvent was removedunder a reduced pressure, and a pale yellow solid was obtained in anamount of 124.3 g. This pale yellow solid was recrystallized withtoluene, and after separating the deposit by filtration, it was dried at80° C. for 40 hours, and 54.5 g of pale yellow styrene derivative(Compound Example c1-1) represented by the following Formula (A8) wasobtained.

The thus obtained Formula (A8) substance was examined under the sameconditions as described in Example A1 and the HPLC purity was found tobe 95.0%.

With respect to the obtained styrene derivative (A8), ¹H-NMR wasconducted under the same conditions as described in Example A1. ¹H-NMRspectral data were as given below and are supportive of the Formula(A8).

δ(ppm)=5.11 (2H, s, —OCH₂—), 5.25 (1H, d, —C═C—H), 5.83 (1H, d, —C═C—H),6.72 (1H, d-d, —C═C—H), 6.80 (1H, t, Ar—H), 7.25 (1H, d, Ar—H),7.34-7.49 (5H, M, Ar—H)

In the foregoing ¹H-NMR, when the proton of 5.11 (2H, s, —OCH₂—) wasirradiated at, a 9.9% nuclear Overhauser effect was observed at thearomatic proton of 7.25 (1H, d, Ar—H).

The obtained styrene derivative (A8) was measured for FT-IR under thesame conditions as Example A1, and the following was observed.

v(cm⁻¹)=3236, 3032, 2879, 2719, 2594, 1666, 1612, 1581, 1464, 1443,1385, 1306, 1246, 1234, 1178, 1162, 1087, 1026, 1018, 908, 862, 837,827, 781, 748, 696, 653, 607, 480.

A measurement was conducted on the obtained styrene derivative (A8) forTG-DTA under the same conditions described in Example A1, and it wasobserved by the measurement that the melting point was 177° C., the heatgeneration temperature was 613° C., the weight loss temperatures were181° C., 413° C. and 593° C.

Elementary analysis was conducted on the obtained styrene derivative(A8) under the same conditions as described in Example A1. Thetheoretical values and the measured values by the elemental analysis aregiven below.

measured values: C, 71.66; H, 4.75; N, 0.00.

theoretical values: C, 71.10; H, 5.22; N, 0.00.

On the obtained styrene derivative (A8) was conducted liquidchromatography/mass spectrometry analysis using the same conditions asdescribed in Example A1. The theoretical values and the measured valuesby the mass spectrometry are given below.

measured values: LC/MC m/z=268.8 [M-H]⁻

theoretical values: m/z=270.09

Example A9

An example of how to synthesize a mixture of4-(4′-vinylbenziloxy)-2-hydroxy benzoic acid and4-(3′-vinylbenziloxy)-2-hydroxy benzoic acid with the help of achloromethylstyrene reagent, which is a mixture of p-chloromethylstyreneand m-chloromethylstyrene will be described.

78.6 g of 2,4-dihydroxy benzoic acid was added to 400 ml of methanolwith stirring, and to this was added 152.0 g of potassium carbonate, andthe solution was stirred for 30 minutes at 60° C. Then, 83.5 g ofchloromethylstyrene (manufactured by AGC Seimi Chemical Co., Ltd.;product name: CMS-P), which is a mixture of p-chloromethylstyrene andm-chloromethylstyrene, was dissolved in 50 ml of methanol, and wasdripped into the above-described solution in the course of one hour.After three-hour reaction under reflux, the solution was allowed to coolto room temperature, and the deposit was filtrated aside and washed withmethanol. The thus obtained residue was added with one liter of waterand turned to pH 1 by chloric acid and subjected to 30 minutes stirring,filtration and washing with water. It was dried at 80° C. for 48 hours,and 76.2 g of white solid styrene derivative (a mixture of CompoundExample b1-1 and Compound Example b2-1) represented by the followingFormula (A9) was obtained.

Thus obtained styrene derivative (A9) was examined for HPLC purity underconditions described in Example A1, and it was found 97.7%.

¹H-NMR measurement was conducted on the obtained styrene derivative (A9)under the same conditions as described in Example A1. ¹H-NMRspectrography data were as follows, and are supportive of the structurerepresented by the Formula (A9).

δ(ppm)=5.14 (12H, s, —CH₂—), 5.25-5.30 (1H, dX2, C—H), 5.81-5.88 (1H,dX2, C—H), 6.35-6.57 (2H, m, Ar—H), 6.68-6.79 (1H, dX2, C—H), 7.32-7.54(4H, m, Ar—H), 7.67-7.70 (1H, dX2, Ar—H)

In the foregoing ¹H-NMR, when the proton of 5.14 (2H, s, —OCH₂—) wasirradiated at, a 16.8-% nuclear Overhauser effect was observed at thearomatic proton of 6.53-6.57.

The obtained styrene derivative (A9) was measured for FT-IR under thesame conditions as Example A1, and the following was observed.

v(cm⁻¹)=3448, 3007, 2864, 2551, 2362, 1655, 1622, 1514, 1454, 1437,1383, 1350, 1250, 1192, 1151, 1095, 1036, 1014, 991, 980, 910, 852, 835,823, 793, 777, 681, 648, 606, 532, 496, 461.

A measurement was conducted on the obtained styrene derivative (A9) forTG-DTA under the same conditions as described in Example A1, and it wasobserved by the measurement that the decalescent point was 157° C., theheat generation temperatures were 440° C. and 570° C., and the weightloss temperatures were 216° C., 434° C. and 542° C.

Elementary analysis was conducted on the obtained styrene derivative(A9) under the same conditions as described in Example A1. Thetheoretical values and the measured values by the elemental analysis aregiven below.

measured values: C, 71.71; H, 5.01; N, 0.00.

theoretical values: C, 71.10; H, 5.22; N, 0.00.

On the obtained styrene derivative (A9) was conducted liquidchromatography/mass spectrometry analysis using the same conditions asdescribed in Example A1. The theoretical values and the measured valuesby the mass spectrometry are given below.

measured values: LC/MC m/z=269.0 [M-H]⁻

theoretical values: m/z=270.09

Example A10

157.3 g of 3,4-dihydroxy benzoic acid was dissolved in 1200 ml ofmethanol with stirring, and 304.1 g of K₂CO₃ was added and stirred at atemperature of 65° C. 175.8 g of 4-chloromethylstyrene was dripped intothe reaction liquid in the course of one hour. The reaction was allowedto proceed under reflux for one hour and the resultant solution wasallowed to cool to the room temperature. The thus obtained deposit wasfiltered aside and was washed with methanol. The residue was dispersedin 2 liters of water of pH 1, and extraction was conducted by addingethyl acetate. Then the ethyl acetate layer was washed with saturatedsaline solution and the ethyl acetate layer was removed, and drying wasconducted with magnesium sulfate, and under a reduced pressure thesolvent was removed. The obtained deposit was recrystallized by means ofethyl acetate, and the deposit was filtered aside. The deposit was driedfor 40 hours at 80° C., and 52.9 g of a white solid styrene derivative(Compound Example d1-1) represented by the following Formula (A10) wasobtained.

The thus obtained Formula (A10) was examined for HPLC purity underconditions described in Example A1, and it was found 96.2%.

With respect to the obtained styrene derivative (A10), ¹H-NMR wasconducted under the same conditions as described in Example A1. ¹H-NMRspectral data were as given below and are supportive of the Formula(A10).

δ(ppm)=5.17 (2H, s, —OCH₂—), 5.27 (1H, d, —C═C—H), 5.85 (1H, d, —C═C—H),6.74 (1H, d-d, —C═C—H), 7.05 (1H, d, Ar—H), 7.35-7.38 (2H, m, Ar—H),7.44 (2H, d, Ar—H), 7.50 (2H, d, Ar—H).

In the foregoing ¹H-NMR, when the proton of 5.17 (2H, s, —OCH₂—) wasirradiated at, a 12.8% nuclear Overhauser effect was observed at thearomatic proton of 7.05 (1H, d, Ar—H).

The obtained styrene derivative (A10) was measured for FT-IR under thesame conditions as Example A1, and the following was observed.

v(cm⁻¹)=3550, 2931, 2877, 2823, 2557, 1884, 1801, 1678, 1620, 1593,1560, 1516, 1473, 1462, 1421, 1379, 1362, 1311, 1286, 1273, 1223, 1188,1130, 1093, 1003, 991, 943, 895, 866, 837, 825, 766, 749, 730, 650, 598,563, 478, 438, 403.

A measurement was conducted on the obtained styrene derivative (A10) forTG-DTA under the same conditions described in Example A1, and it wasobserved by the measurement that the melting point was 197° C., the heatgeneration temperature was 611° C., the weight loss temperatures were175° C., 230° C., 410° C. and 570° C.

Elementary analysis was conducted on the obtained styrene derivative(A10) under the same conditions as described in Example A1. Thetheoretical values and the measured values by the elemental analysis areas follows.

measured values: C, 73.97; H, 6.92; N, 0.00.

theoretical values: C, 73.60; H, 6.79; N, 0.00.

On the obtained styrene derivative (A10) was conducted liquidchromatography/mass spectrometry analysis using the same conditions asdescribed in Example A1. The theoretical values and the measured valuesby the mass spectrometry are given below.

measured values: LC/MC m/z=268.93 [M-H]⁻

theoretical values: m/z=270.09

Example A11

157.3 g of 3,4-dihydroxy benzoic acid and 1532.2 g of 80% sulfuric acidwere mixed at a heating temperature of 60° C., and 890.5 g oftert-butanol was added to this dispersion in the course of 45 minutes,and the liquid was stirred for 30 minutes at a temperature of 65° C.Thereafter, the liquid was gradually poured into 2 kg of ice water, towhich 1 liter of toluene was added, and the resultant deposit wasfiltered aside and washed with water. Then the deposit was filteredaside and dried at 80° C., and 160.0 g of tert-butylated salicylic acidintermediate was obtained.

63.1 g of the thus obtained salicylic acid intermediate was dissolved in250 ml of methanol with stirring, and 91.21 g of potassium carbonate wasadded and heated at 62° C. To this reaction liquid was added 52.6 g of4-(chloromethyl)styrene in the course of 45 minutes, and a reaction wasallowed to proceed for three hours at 67° C. The resultant reactionsolution was cooled, and the deposit was filtered aside, and washed withmethanol.

The obtained residue after the filtration was dispersed in 1.5 liters ofwater of pH 2, and was extracted with ethyl acetate. Then the solutionwas separated and added with water for washing, and the ethyl acetatelayer was removed and dried with magnesium sulfate, and the ethylacetate was removed under a reduced pressure and a deposit was obtained.The thus obtained deposit was recrystallized with toluene, and thedeposit was filtered aside and dried for 44 hours at 80° C., and 47.5 gof a styrene derivative (Compound Example f1-1) represented by thefollowing Formula (A11) was obtained.

The thus obtained styrene derivative (All) was examined under the sameconditions as described in Example A1 and the HPLC purity was found tobe 97.9%.

With respect to the obtained styrene derivative (A11), ¹H-NMR wasconducted under the same conditions as described in Example A1. ¹H-NMRspectral data were as given below and are supportive of the Formula(A11).

δ(ppm)=1.37 (9H, s, —C(CH₃)₃), 5.21 (2H, s, —OCH₂—), 5.26 (1H, d,—C═C—H), 5.85 (1H, d, —C═C—H), 6.73 (1H, d-d, Ar—H), 7.41, 7.49 (5H, s,Ar—H)

In the foregoing ¹H-NMR, when the proton of 5.21 (2H, s, —OCH₂—) wasirradiated at, an 8.3% nuclear Overhauser effect was observed at thearomatic proton of 7.41 (1H, s, Ar—H).

The obtained styrene derivative (All) was measured for FT-IR under thesame conditions as Example A1, and the following was observed.

v(cm⁻¹)=3518, 2956, 2598, 1678, 1630, 1605, 1516, 1489, 1427, 1387,1360, 1302, 1255, 1215, 1171, 1117, 1047, 1018, 993, 943, 918, 858, 841,829, 808, 769, 762, 735, 698, 652, 555, 490.

A measurement was conducted on the obtained styrene derivative (A11) forTG-DTA under the same conditions described in Example A1, and it wasobserved by the measurement that the melting point was 175° C., the heatgeneration temperature was 579° C., the weight loss temperatures were139° C., 221° C., 300° C., 413° C., and 544° C.

Elementary analysis was conducted on the obtained styrene derivative(A11) under the same conditions as described in Example A1. Thetheoretical values and the measured values by the elemental analysis aregiven below.

measured values: C, 74.00; H, 6.92; N, 0.00.

theoretical values: C, 73.60; H, 6.79; N, 0.00.

On the obtained styrene derivative (A11) was conducted liquidchromatography/mass spectrometry analysis using the same conditions asdescribed in Example A1. The theoretical values and the measured valuesby the mass spectrometry are given below.

measured values: LC/MC m/z=325.20 [M-H]⁻

theoretical values: m/z=326.15

Example A12

46.23 g of 2,5-dihydroxy benzoic acid and 460 g of 80% sulfuric acidwere mixed at heating temperature of 70° C., and to this dispersionliquid was added 78.15 g of 2-octanol in the course of 10 minutes andthe liquid was stirred for 30 minutes at 70° C. Thereafter, this processof adding 78.15 g of 2-octanol to the dispersion liquid followed by 30minutes stirring was repeated twice. After the 30 minutes stirring, thereaction liquid was cooled to the room temperature, and was graduallypoured into 3 kg of ice water. The obtained deposit was filtered aside,washed with water and then with hexane. The resultant residue wasdissolved in 500 ml of methanol, and reprecipitated in 4.5 liters ofwater. After a filtration, the residue was dried for 24 hours at 80° C.,and the reaction product was subjected to silica gel columnchromatography, and 29.3 g of octylated salicylic acid intermediate wasobtained in a hexane:toluene fraction.

The thus obtained salicylic acid intermediate in an amount of 25.0 g wasdissolved in 150 ml of methanol while being stirred, and 29.1 g ofpotassium carbonate was added and heating was conducted at 65° C. Tothis reaction liquid was dripped a mixture of 14.7 g of4-(chloromethyl)styrene and 100 ml of methanol with stirring, and areaction was allowed to proceed for three hours at 65° C. The thusobtained reaction liquid was cooled, filtrated, and the methanol in thefiltrate was removed by distillation under a reduced pressure and adeposit was obtained.

The obtained deposit was dispersed in 1.5 liters of water of pH 2, andextraction was conducted by adding ethyl acetate. Thereafter, thesolution was separated and added with water with which it was washed,and after the ethyl acetate layer was separated, it was dried withmagnesium sulfate, and the ethyl acetate was removed by distillationunder a reduced pressure, and a deposit was obtained. The obtaineddeposit was washed with hexane and filtrated aside, and the residue wasrecrystallized by using a mixed solution of toluene and ethyl acetate.The deposit was filtered aside and dried at 80° C. for 45 hours, and24.1 g of styrene derivative (Compound Example a1-3) represented by thefollowing Formula (A12) was obtained.

The thus obtained styrene derivative (A12) was examined for HPLC purityunder conditions described in Example A1, and it was found 96.2%.

With respect to the obtained styrene derivative (A12), ¹H-NMR wasconducted under the same conditions as described in Example A1 exceptthat CDCl₃ was used as the measurement solvent. ¹H-NMR spectral datawere as given below and are supportive of the Formula (A12).

δ(ppm)=0.95 (3H, t, —CH₃), 1.18-1.51 (16H, broad, —(CH₂)₆—, —CH₃), 3.79(1H, m, 5.02 (2H, s, —OCH₂—), 5.24 (1H, d, C—H), 5.78 (1H, d, C—H), 6.69(1H, d-d, —CH═), 7.24 (1H, d, Ar—H), 7.32 (1H, d, Ar—H), 7.42 (1H, d,Ar—H), 7.44 (1H, d, Ar—H)

In the foregoing ¹H-NMR, when the proton of 5.02 (2H, s, —OCH₂—) wasirradiated at, a 8.1% nuclear Overhauser effect was observed at thearomatic proton of 7.24 (1H, d, Ar—H).

The obtained styrene derivative (A12) was measured for FT-IR under thesame conditions as Example A1, and the following was observed.

v(cm⁻¹)=3425, 3111, 3004, 2966, 2932, 2875, 2866, 2734, 2654, 1911,1824, 1801, 1766, 1715, 1659, 1624, 1611, 1610, 1521, 1497, 1459, 1463,1411, 1411, 1378, 1365, 1320, 1290, 1278, 1227, 1201, 1178, 1156, 1069,1040, 986, 965, 941, 900, 893, 847, 844, 822, 808, 795, 722, 685, 660,610, 524, 522, 499, 468, 422.

A measurement was conducted on the obtained styrene derivative (A12) forTG-DTA under the same conditions described in Example A1, and it wasobserved by the measurement that the melting point was 166° C., the heatgeneration temperatures were 514° C. and 557° C., the weight losstemperatures were 377° C. and 537° C.

Elementary analysis was conducted on the obtained styrene derivative(A12) under the same conditions as described in Example A1. Thetheoretical values and the measured values by the elemental analysis aregiven below.

measured values: C, 74.10; H, 7.85; N, 0.00.

theoretical values: C, 75.36; H, 7.91; N, 0.00.

On the obtained styrene derivative (A12) was conducted liquidchromatography/mass spectrometry analysis using the same conditions asdescribed in Example A1. The theoretical values and the measured valuesby the mass spectrometry are given below.

measured values: LC/MC m/z=379.9 [M-H]⁻

theoretical values: m/z=382.5

Example A13

An example of how to synthesize a mixture of5-(4′-vinylbenziloxy)-3-tert-butyl-2-hydroxy benzoic acid and5-(2′-vinylbenziloxy)-3-tert-butyl-2-hydroxy benzoic acid with the helpof a chloromethylstyrene reagent, which is a mixture ofp-chloromethylstyrene and m-chloromethylstyrene will be described.

25.0 g of 3-tert-butyl-2,5-dihydroxy benzoic acid, which is thesalicylic acid intermediate obtained in Example A2 was dissolved in 150ml of methanol with stirring, and to this was added 40.0 g of potassiumcarbonate, and the solution was stirred for one hour at 60° C. Then,23.4 g of chloromethylstyrene (product name 4-Chloromethyl Styrene;manufactured by CHANGZHOU WUJIN LINCHUAN CHEMICAL CO., LTD.), which is amixture of p-chloromethylstyrene and o-chloromethylstyrene, wasdissolved in 100 ml of methanol, and was dripped into theabove-described solution and a reaction was allowed to proceed for threehours at 65° C. The reaction liquid thus obtained was allowed to cool toroom temperature, and the deposit was filtrated aside and washed withmethanol. The thus obtained residue was added with one liter of waterand turned to pH 1 by chloric acid and subjected to 30 minutes stirring,filtration and washing with water. It was dried at 80° C. for 48 hours,and 23.2 g of white solid styrene derivative (a mixture of CompoundExample a1-2 and Compound Example a3-2) represented by the followingFormula (A13) was obtained.

Thus obtained styrene derivative (A13) was examined for HPLC purityunder conditions described in Example A1, and it was 97.7%.

¹H-NMR measurement was conducted on the obtained styrene derivative(A13) under the same conditions as described in Example A1 except thatCDCl₃ was used as the measurement solvent. ¹H-NMR spectrography datawere as follows, and are supportive of the structure represented by theFormula (A13).

δ(ppm)=1.51-1.55 (9H, sx2, —C(CH₃)₃), 5.22-5.29 (1H, dx2, C—H),5.80-5.87 (1H, dx2, C—H), 6.55-6.60 (2H, m, Ar—H), 6.70-6.81 (H, dx2,C—H), 7.36-7.58 (4H, m, Ar—H), 7.62-7.71 (1H, m, Ar—H)

In the foregoing ¹H-NMR, when the proton of 5.22-5.29 (1H, dx2, C—H) wasirradiated at, a 15.5% nuclear Overhauser effect was observed at thearomatic proton of 6.55-6.60 (2H, m, Ar—H).

The obtained styrene derivative (A13) was measured for FT-IR under thesame conditions as Example A1, and the following was observed.

v(cm⁻¹)=3420, 3004, 2966, 2709, 2622, 1893, 1822, 1790, 1778, 1756,1655, 1633, 1612, 1511, 1487, 1470, 1421, 1411, 1396, 1377, 1365, 1322,1300, 1280, 1200, 11880, 1115, 966, 957, 910, 890, 832, 811, 804, 795,723, 678, 659, 604, 525, 514, 467, 422.

A measurement was conducted on the obtained styrene derivative (A13) forTG-DTA under the same conditions described in Example A1, and it wasobserved by the measurement that the decalescent point was 151° C., theheat generation temperatures were 433° C. and 549° C., and the weightloss temperatures were 209° C., 444° C. and 553° C.

Elementary analysis was conducted on the obtained styrene derivative(A13) under the same conditions as described in Example A1. Thetheoretical values and the measured values by the elemental analysis aregiven below.

measured values: C, 69.57; H, 5.61; N, 0.00.

theoretical values: C, 71.82; H, 5.67; N, 0.00.

On the obtained styrene derivative (A13) was conducted liquidchromatography/mass spectrometry analysis using the same conditions asdescribed in Example A1. The theoretical values and the measured valuesby the mass spectrometry are given below.

measured values: LC/MC m/z=283.86 [M-H]⁻

theoretical values: m/z=284.31

Examples of how to synthesize esterified styrene derivative of thepresent invention will be explained in Examples A14 through A15.

Example A14

50.44 g of 2,4-dihydroxy benzoic acid methyl ester was dissolved bybeing stirred in 300 ml of methanol, and this was added with 62.2 g ofpotassium carbonate and heated to 60° C. Into this reaction liquid wasdripped 53.0 g of 4-(chloromethyl)styrene, and a reaction was allowed toproceed for 4.5 hours at 65° C. This reaction liquid was cooled,filtrated, and the methanol in the filtrate was removed by distillationunder a reduced pressure and a deposit was obtained.

The obtained deposit was dispersed in 1.5 liters of water of pH 2, andextraction was conducted by adding ethyl acetate. Thereafter, thesolution was separated and added with water with which it was washed,and after the ethyl acetate layer was separated, it was dried withmagnesium sulfate, and the ethyl acetate was removed by distillationunder a reduced pressure, and a deposit was obtained. The thus obtaineddeposit was recrystallized by using methanol. After the deposit wasfiltered aside, it was dried for 20 hours at 80° C., and 17.2 g ofstyrene derivative (Compound Example b1-23) represented by the followingFormula (A14) was obtained.

The thus obtained styrene derivative (A14) was examined for HPLC purityunder conditions described in Example A1, and it was found 98.0%.

With respect to the obtained styrene derivative (A14), ¹H-NMR wasconducted under the same conditions as described in Example A1 exceptthat CDCl₃ was used as the measurement solvent. ¹H-NMR spectral datawere as given below and are supportive of the Formula (A14).

δ(ppm)=3.86 (3H, s, —OCH), 5.16 (2H, s, —OCH₂—), 5.28 (1H, d, C—H), 5.85(1H, d, C—H), 6.58-6.62 (2H, m, Ar—H), 6.74 (1H, d-d, —CH═), 7.42 (2H,d, Ar—H), 7.50 (2H, d, Ar—H), 7.72 (1H, d, Ar—H), 10.77 (1H, s, —OH)

In the foregoing ¹H-NMR, when the proton of 5.16 (2H, s, —OCH₂—) wasirradiated at, a 12.5% nuclear Overhauser effect was observed at thearomatic proton of 7.24 (2H, d, Ar—H).

The obtained styrene derivative (A14) was measured for FT-IR under thesame conditions as Example A1, and the following was observed.

v(cm⁻¹)=3180, 3091, 2954, 1907, 1824, 1668, 1620, 1579, 1514, 1504,1489, 1468, 1439, 1408, 1383, 1346, 1298, 1258, 1215, 1178, 1144, 1095,1005, 985, 978, 958, 945, 910, 862, 843, 827, 785, 735, 702, 650, 634,588, 532, 486, 463.

The measurement result by FT-IR is shown in FIG. 9.

A measurement was conducted on the obtained styrene derivative (A14) forTG-DTA under the same conditions described in Example A1, and the resultis shown in FIG. 10. It was observed by the measurement that the meltingpoint was 85.5° C., the heat generation temperatures were 450° C. and569° C., the weight loss temperatures were 196° C., 369° C., 445° C. and568° C.

Elementary analysis was conducted on the obtained styrene derivative(A14) under the same conditions as described in Example A1. Thetheoretical values and the measured values by the elemental analysis aregiven below.

measured values: C, 72.03; H, 5.70; N, 0.00.

theoretical values: C, 71.82; H, 5.67; N, 0.00.

On the obtained styrene derivative (A14) was conducted liquidchromatography/mass spectrometry analysis using the same conditions asdescribed in Example A1. The theoretical values and the measured valuesby the mass spectrometry are given below.

measured values: LC/MC m/z=283.1 [M-H]⁻

theoretical values: m/z=284.1

Example A15

50.0 g of 2,5-dihydroxy benzoic acid butyl ester was dissolved in 200 mlof methanol with stirring, and 73.2 g of potassium carbonate was addedand heated at 60° C. 37.0 g of 4-(chloromethyl)styrene was dripped intothis reaction liquid, and a reaction was allowed to proceed for 5.0 hourat 65° C. The thus obtained reaction liquid was cooled, and filtered andthe methanol in the filtrate was removed by distillation under a reducedpressure and a deposit was obtained.

The obtained deposit was dispersed in 1.5 liters of water of pH 2, andwas extracted with ethyl acetate. Then, the solution was separated, andadded with water for washing, and the ethyl acetate layer was separatedand dried with magnesium sulfate, and the ethyl acetate was distilledoff under a reduced pressure, and a deposit was obtained. The thusobtained deposit was recrystallized with methanol. After filtering asidethe deposit, it was dried for 20 hours at 80° C., and 15.2 g of astyrene derivative (Compound Example a1-28) represented by the followingFormula (A15).

The thus obtained styrene derivative (A15) was examined for HPLC purityunder conditions described in Example A1, and it was found 97.7%.

With respect to the obtained styrene derivative (A15), ¹H-NMR wasconducted under the same conditions as described in Example A1 exceptthat CDCl₃ was used as the measurement solvent. ¹H-NMR spectral datawere as given below and are supportive of the Formula (A15).

δ(ppm)=1.12 (3H, t, —CH₃), 1.23-1.44 (2H, m, —CH₂—), 1.56-1.95 (2H, m,—CH₂—), 4.21 (2H, t, —CH₂—), 5.15 (2H, s, —OCH₂—), 5.25 (1H, d, C—H),5.86 (1H, d, C—H), 6.38-6.41 (2H, m, Ar—H), 6.71 (1H, d-d, —CH═), 7.40(2H, d, Ar—H), 7.48 (2H, d, Ar—H), 7.63 (1H, d, Ar—H)

In the foregoing ¹H-NMR, when the proton of 5.15 (2H, s, —OCH₂—) wasirradiated at, a 13.8% nuclear Overhauser effect was observed at thearomatic proton of 7.40 (214, d, Ar—H).

The obtained styrene derivative (A15) was measured for FT-IR under thesame conditions as Example A1, and the following was observed.

v(cm⁻¹)=3177, 3086, 2946, 1911, 1832, 1670, 1622, 1581, 1522, 1493,1477, 1428, 1400, 1375, 1343, 1301, 1261, 1209, 1169, 1146, 1099, 1004,978, 936, 910, 858, 837, 789, 732, 699, 647, 629, 584, 536, 458

A measurement was conducted on the obtained styrene derivative (A15) forTG-DTA under the same conditions described in Example A1, and it wasobserved by the measurement that the melting point was 73.8° C., theheat generation temperatures were 443° C. and 549° C., the weight losstemperatures were 176° C., 349° C. and 558° C.

Elementary analysis was conducted on the obtained styrene derivative(A15) under the same conditions as described in Example A1. Thetheoretical values and the measured values by the elemental analysis aregiven below.

measured values: C, 72.78; H, 6.71; N, 0.00.

theoretical values: C, 73.60; H, 6.79; N, 0.00.

On the obtained styrene derivative (A15) was conducted liquidchromatography/mass spectrometry analysis using the same conditions asdescribed in Example A1. The theoretical values and the measured valuesby the mass spectrometry are given below.

measured values: LC/MC m/z=325.5 [M-H]⁻

theoretical values: m/z=326.1

Examples of how a charge control resin (copolymer) of the presentinvention is synthesized will be explained in Examples B1 through B26.

Example B1 Preparation of a Combination of the Formula (A2) Plus Styrenein a Molar Ratio of 5.0:95.0

9.91 g of the styrene derivative (A2) obtained in Example A2 and 60.09 gof styrene were dissolved in 42 ml of toluene and stirred for one hour.Then, this was heated to 110° C. in an atmosphere of a nitrogen gasstream (50 ml/min). To this solution was dripped in the course of 22minutes a mixture liquid of 42 ml of toluene and 4.62 g of tert-butylperoxy isopropyl monocarbonate (PERBUTYL I, a product name of NOFCORPORATION). After a reaction was allowed to proceed for four hours at110° C., the liquid was cooled and dripped into one liter of methanol,and a white deposit was obtained. This reaction liquid was filtered andthus obtained deposit was dissolved in 300 ml of tetrahydrofuran.Thereafter, this was dripped into 1.5 liters of methanol and a whitedeposit was caused to precipitate and was filtered aside. This residuewas dried at 90° C. under a reduced pressure, and 57.56 g of a copolymer(B1) was obtained from the styrene derivative and the styrene.

The obtained copolymer (B1) was examined by means of ¹H-NMR (nuclearmagnetic resonance apparatus: FT-NMR JNM-AL 300 manufactured by JEOLLtd.) under conditions where the resonance frequency was 300 MHz, themeasurement nuclide was ¹H, the used solvent was CDCl₃, and themeasurement temperature was room temperature. The result of themeasurement by ¹H-NMR is shown in FIG. 11.

There were observed no peaks that should, respectively, represent thevinyl group of the styrene and the styrene derivative (A2) representedby the Formula (A2) as a starting materials before the copolymerizationreaction, and broad aromatic proton(s) and alkyl chain(s) were observed,and furthermore, a broad hydroxyl group originating from the styrenederivative A2 and a broad proton of δ(ppm)=4.9 (—CH₂—O—) were observed.From the integrated values of the peaks, it was confirmed that theconstituent unit obtained from the styrene derivative (A2) was containedin the obtained copolymer by 4.69%.

The obtained copolymer (B1) was subjected to KBr method measurement,using an FT-IR (Fourier transform infrared spectrophotometer (JIR-SPX60Smanufactured by JEOL Ltd.)), and the following observation was made.

v(cm⁻¹)=3455, 3082, 3061, 3026, 2922, 2850, 1942, 1867, 1799, 1741,1674, 1601, 1493, 1452, 1362, 1265, 1201, 1155, 1030, 906, 798, 756,698, 540

The result of the measurement by the FT-IR is shown in FIG. 12.

The obtained copolymer (B1) is composed of Unit A included in theFormula (5), which is a constituent unit obtained from Compound Examplea1-2, and Unit B, which is a constituent unit represented by the Formula(9).

With regard to the obtained copolymer (B1), a measurement was conductedby a differential thermal/thermogravimetry simultaneous analyzerTG-DTA6200 EXSTAR6000, manufactured by SII Nanotechnology Inc., under acondition whereby temperature was raised from 30° C. to 550° C. at arate of 10° C./minute. The measurement result of the simultaneousthermogravimetric and differential thermal analysis (TG-DTA) is as shownin FIG. 13. It was observed by the measurement that the weight losstemperatures were 345° C. and 513° C., and the heat generatingtemperatures were 337° C. and 535° C.

The molecular weight distribution of the obtained copolymer (B1) wasmeasured by Gel Permeation Chromatography (manufactured by ShimadzuCorporation; detector: RID-10A; column oven: CTO-20A; pump: LC-20AT;degasser: DGU-20A₅) under the following conditions, and the moleculardistribution, number average molecular weight, and weight averagemolecular weight were determined.

The GPC measurement conditions were such that 5 mg of the tested samplewas dissolved in 5 ml of tetrahydrofuran, and it was passed through asolvent-resistant membrane filter having a pore diameter of 0.5micrometer and the filtrate was used as the sample solution to beanalyzed in the following manner.

column: ultra high speed SEC (size exclusion) semi-micro GPC column

elimination limit molecular quantity: polystyrene 4×10⁶ (TSKgel SuperHM-M, manufactured by Tosho Corp.) 2 units

The calculation for the molecular weight of the sample was based on acalibration curve created with reference to a standard polystyrene(Shodex STANDARD SM-105 (S-3730, S-2480, S-1230, S-579, S-197, S-551,S-31.4, S-12.8, S-3.95, S-1.20) manufactured by Showa Denko K.K.)).

The measurement result of the molecular weight distribution of thecopolymer (B1) as measured under the above-described conditions is shownin FIG. 14. It was confirmed from the result of the measurement that thenumber average molecular weight (Mn) was 16160, the weight averagemolecular weight (Mw) was 66496, and the ratio of the molecular weightdistribution (Mw/Mn) was 4.1.

In an elementary analysis, it is possible to predict a ratio of aparticular monomer that would occupy the resulting copolymer from theelementary analysis measurement result of the starting monomer and thatof the copolymer. Elementary analysis was conducted on the obtainedcopolymer (B1) under the same conditions as described in Example A1. Thetheoretical values and the measured values by the elemental analysis areas given below.

measured values: C, 89.45; H, 7.69; N, 0.00; O, 2.84.

theoretical values: C, 89.60; H, 7.62; N, 0.00; O, 2.78.

Here, the value for oxygen was calculated by subtracting the values forcarbon (C), hydrogen (H) and nitrogen (N) from the totality of 100%. Theresult of the measurement was commensurate with the theoretical valuespredicted in the case where the styrene derivative (A2) was assumed tobe contained in the copolymer by 5%.

The glass transition temperature of the obtained copolymer (B1) wasmeasured by a differential scanning calorimeter DSC6200 EXSTAR6000manufactured by SII Nanotechnology Inc., under following conditions, andthe glass transition temperature was determined.

The conditions for the measurement of the glass transition temperaturewere such that the measured sample was heated to 170° C., and cooledquickly, and then the temperature was raised from 30° C. to 170° C., ata rate of 10° C./minute. The result of the measurement of the glasstransition temperature is shown in FIG. 15. According to the result, theglass transition temperature of the copolymer (B1) was 104.0° C.

The volume resistive value of the obtained copolymer (B1) was measuredby a digital ultra-high resistance/micro ammeter R8340A manufactured byADVANTEST CORPORATION, under the following conditions, and the volumeresistive value was determined.

The conditions for the volume resistive value measurement were asprescribed in JIS (K6911) and as follows.

Applied voltage and time: 500 v; one minute

Electrode: chief electrode 38 mm diameter;

Load: 2000 kg;

Test atmosphere: temperature 23+/−2° C.;

Humidity: 50+/−5 RH.

As the result of the measurement, the copolymer (B1) was found to have avolume specific resistivity of 1.3×10¹⁶ Ωcm.

Example B2 Preparation of a Combination of the Formula (A2) Plus Styrenein a Molar Ratio of 5.0:95.0

9.91 g of the styrene derivative (A2) and 60.09 g of styrene weredispersed in 42 ml of toluene, and this was heated to 110° C. in anatmosphere of a nitrogen gas stream (50 ml/min). To this solution wasdripped in the course of 3 minutes a mixture liquid of 42 ml of tolueneand 4.62 g of tert-butyl peroxyisopropyl monocarbonate (PERBUTYL I, aproduct name of NOF CORPORATION). After a reaction was allowed toproceed for four hours at 110° C., the liquid was cooled. The reactionliquid was dripped into one liter of methanol, and a white deposit wasobtained, and it was filtered aside, and this residue was dried at 60°C. under a reduced pressure for 10 hours, and 29.5 g of a copolymer (B2)was obtained.

The obtained copolymer (B2) was examined by means of ¹H-NMR under thesame conditions as described in Example B1, and there were observed nopeaks that should, respectively, represent the vinyl group of thestyrene and the styrene derivative (A2) represented by the Formula (A2)as a starting materials before the copolymerization reaction, whereasbroad aromatic proton(s) and alkyl chain(s) were observed, andfurthermore, a broad hydroxyl group originating from the styrenederivative (A2) and a broad proton of δ(ppm)=4.9 (—CH₂—O—) wereobserved. From the integrated values of the peaks, it was determinedthat the constituent unit obtained from the styrene derivative (A2) wascontained in the obtained copolymer by 4.38%.

The obtained copolymer (B2) was subjected to FT-IR analysis under thesame conditions as described in Example B1, and the followingobservation was made.

v(cm⁻¹)=3425, 3081, 3061, 3025, 2922, 2850, 1942, 1869, 1801, 1741,1673, 1603, 1493, 1452, 1363, 1265, 1201, 1155, 1030, 906, 756, 698,540.

A measurement was conducted on the obtained copolymer (B2) for TG-DTAunder the same conditions described in Example B1. The result of theTG-DTA measurement is shown in FIG. 16. The measurement result showsthat the heat generation temperatures were 388° C. and 538° C., and theweight loss temperatures were 330° C. and 513° C.

The obtained copolymer (B2) was subjected to GPC measurement under thesame conditions as described in Example B1. The measurement result ofthe molecular weight distribution of the copolymer (B2) as measuredunder the above-described conditions is shown in FIG. 17. It wasconfirmed from the result of the measurement that the copolymer (B2) hasa number average molecular weight (Mn) of 6861, a weight averagemolecular weight (Mw) of 14225, and a molecular weight distributionratio (Mw/Mn) of 2.1.

The glass transition temperature of the obtained copolymer (B2) wasmeasured under the same conditions as described in Example B1. Theresult of the measurement determined the glass transition temperature ofthe copolymer (B2) to be 99.02° C.

Example B3 Preparation of a Combination of the Formula (A2) Plus Styrenein a Molar Ratio of 5.0:95.0

9.91 g of the styrene derivative (A2) and 60.09 g of styrene weredispersed in 21 ml of toluene, and this was heated to 110° C. in anatmosphere of a nitrogen gas stream (50 ml/min) To this solution wasdripped in the course of 36 minutes a mixture liquid of 21 ml of tolueneand 4.62 g of tert-butyl peroxy isopropyl monocarbonate (PERBUTYL I, aproduct name of NOF CORPORATION). After a reaction was allowed toproceed for 1.5 hour at 110° C., the liquid was cooled. The obtainedreaction liquid was dissolved in 300 ml of tetrahydrofuran, and drippedin one liter of methanol, and a precipitate occurred. The reactionliquid was passed through a filter and the residue was dried for 20hours at 90° C. under a reduced pressure, and 14.89 g of a copolymer(B3) was obtained.

The obtained copolymer (B3) was examined by means of ¹H-NMR under thesame conditions as described in Example B1, and there were observed nopeaks that should, respectively, represent the vinyl group of thestyrene and the styrene derivative (A2) represented by the Formula (A2)as a starting materials before the copolymerization reaction, whereasbroad aromatic proton(s) and alkyl chain(s) were observed, andfurthermore, a broad hydroxyl group originating from the styrenederivative (A2) and a broad proton of δ(ppm)=4.91 (—CH₂—O—) wereobserved. From the integrated values of the peaks, it was determinedthat the constituent unit obtained from the styrene derivative (A2) wascontained in the obtained copolymer by 4.59%.

The obtained copolymer (B3) was subjected to FT-IR analysis under thesame conditions as described in Example B1, and the followingobservation was made.

v(cm⁻¹)=3435, 3082, 3061, 3026, 2922, 2850, 1942, 1871, 1741, 1678,1601, 1583, 1493, 1452, 1437, 1363, 1265, 1201, 1180, 1155, 1099, 1030,906, 798, 756, 698, 540.

A measurement was conducted on the obtained copolymer (B3) for TG-DTAunder the same conditions described in Example B1. The result of themeasurement is shown in FIG. 18. The measurement result shows that theheat generation temperatures were 358° C. and 537° C., and the weightloss temperatures were 343° C. and 515° C.

The obtained copolymer (B3) was subjected to GPC measurement under thesame conditions as described in Example B1. The measurement result ofthe molecular weight distribution of the copolymer (B3) as measuredunder the above-described conditions is shown in FIG. 19. It wasconfirmed from the result of the measurement that the copolymer (B3) hasa number average molecular weight (Mn) of 22178, a weight averagemolecular weight (Mw) of 437142, and a molecular weight distributionratio (Mw/Mn) of 19.7.

The glass transition temperature of the obtained copolymer (B3) wasmeasured in the same manner as described in Example B1. The result ofthe measurement determined the glass transition temperature of thecopolymer (B3) to be 102.7° C.

The volume resistive value of the copolymer (B3) was measured in thesame manner as described in Example B1. The result of the measurementwas that the copolymer (B3) had a volume resistive value of 1.1×10¹⁷Ωcm.

Example B4 Preparation of a Combination of the Formula (A2) Plus Styrenein a Molar Ratio of 1.0:99.0

1.07 g of the styrene derivative (A2) and 33.93 g of styrene weredispersed in 21 ml of toluene, and this was heated to 110° C. in anatmosphere of a nitrogen gas stream (50 ml/min). To this solution wasdripped in the course of 17 minutes a mixture liquid of 21 ml of tolueneand 2.31 g of tert-butyl peroxy isopropyl monocarbonate (PERBUTYL I, aproduct name of NOF CORPORATION). After a reaction was allowed toproceed for 4.0 hours at 110° C., the liquid was cooled. The obtainedreaction liquid was added to 500 ml of methanol to cause aprecipitation, and a highly viscous white deposit was obtained. Afterremoving a supernatant methanol, the deposit was dissolved in 150 ml oftetrahydrofuran, and the solution was added to 2 liters of methanol tooccasion a precipitation and the precipitate was filtered aside. Then,the substance was washed by being sprinkled twice with 200 ml ofmethanol and the residue was dried at 80° C. under a reduced pressurefor 30 hours, and 32.66 g of a copolymer (B4) was obtained.

The obtained copolymer (B4) was examined by means of ¹H-NMR under thesame conditions as described in Example B1, and there were observed nopeaks that should, respectively, represent the vinyl group of thestyrene and the styrene derivative (A2) represented by the Formula (A2)as a starting materials before the copolymerization reaction, whereasbroad aromatic proton(s) and alkyl chain(s) were observed, andfurthermore, a broad hydroxyl group originating from the styrenederivative (A2) and a broad proton of δ(ppm)=4.90 (—CH₂—O—) wereobserved. From the integrated values of the peaks, it was determinedthat the constituent unit obtained from the styrene derivative (A2) wascontained in the obtained copolymer by 0.48%.

The obtained copolymer (B4) was subjected to FT-IR analysis under thesame conditions as described in Example B1, and the followingobservation was made.

v(cm⁻¹)=3433, 3082, 3061, 3026, 3001, 2922, 2848, 1944, 1871, 1803,1741, 1601, 1583, 1493, 1452, 1375, 1327, 1263, 1200, 1182, 1155, 1068,1028, 980, 964, 906, 841, 756, 698, 621, 540.

A measurement was conducted on the obtained copolymer (B4) for TG-DTAunder the same conditions described in Example B1. The result of themeasurement shows that the heat generation temperature was 345° C., andthe weight loss temperatures were 339° C. and 512° C.

The obtained copolymer (B4) was subjected to GPC measurement under thesame conditions as described in Example B1. The measurement result showsthat the copolymer (B4) had a number average molecular weight (Mn) of11184, a weight average molecular weight (Mw) of 28845, and a molecularweight distribution ratio (Mw/Mn) of 2.6.

Elementary analysis was conducted on the obtained copolymer (B4) underthe same conditions as described in Example A1. The theoretical valuesand the measured values by the elemental analysis are as given below.

measured values: C, 91.43; H, 7.76; N, 0.00; O, 0.81.

theoretical values: C, 91.67; H, 7.73; N, 0.00; O, 0.60.

The value for oxygen was calculated in the same manner as in Example B1.The result of the measurement was commensurate with the theoreticalvalues predicted in the case where the styrene derivative (A2) wasassumed to be contained in the copolymer by 1%.

The glass transition temperature of the obtained copolymer (B4) wasmeasured in the same manner as described in Example B1. The result ofthe measurement determined the glass transition temperature of thecopolymer (B4) to be 92.57° C.

The volume resistive value of the copolymer (B4) was measured in thesame manner as described in Example B1. The result of the measurementwas that the copolymer (B4) had a volume resistive value of 0.67×10¹⁶Ωcm.

Example B5 Preparation of a Combination of the Formula (A2) Plus Styrenein a Molar Ratio of 10.0:90.0

9.04 g of the styrene derivative (A2) and 25.96 g of styrene weredispersed in 21 ml of toluene, and this solution was heated to 110° C.in an atmosphere of a nitrogen gas stream (50 ml/min). To this solutionwas dripped in the course of 20 minutes a mixture liquid of 21 ml oftoluene and 2.31 g of tert-butyl peroxy isopropyl monocarbonate(PERBUTYL I, a product name of NOF CORPORATION). After a reaction wasallowed to proceed for 4.0 hours at 110° C., the liquid was cooled. Theobtained reaction liquid was added to 500 ml of methanol to cause aprecipitation, and a highly viscous white deposit was obtained. Afterremoving a supernatant methanol, the deposit was dissolved in 150 ml oftetrahydrofuran, and the solution was added to 2 liters of methanol tooccasion a precipitation and the precipitate was filtered aside. Then,the substance was washed by being sprinkled twice with 200 ml ofmethanol and the residue was dried at 90° C. under a reduced pressurefor 10 hours, and 19.03 g of a copolymer (B5) was obtained.

The obtained copolymer (B5) was subjected to an examination by means of¹H-NMR under the same conditions as described in Example B1, but thecopolymer did not solve in heavy chloroform or DMSO (dimethylsulfoxide)d-6 or the like, which were used as the measurement solvent, so that themeasurement was not possible.

The obtained copolymer (B5) was subjected to FT-IR analysis under thesame conditions as described in Example B1, and the followingobservation was made.

v(cm⁻¹)=3427, 3103, 3082, 3061, 3026, 3001, 2922, 2852, 1944, 1871,1803, 1741, 1680, 1659, 1603, 1543, 1512, 1493, 1452, 1435, 1392, 1363,1271, 1201, 1182, 1155, 1099, 1041, 1032, 1018, 964, 906, 843, 820, 798,758, 698, 619, 598, 540.

A measurement was conducted on the obtained copolymer (B5) for TG-DTAunder the same conditions described in Example B1. The result of themeasurement shows that the heat generation temperatures were 355° C. and535° C., and the weight loss temperatures were 244° C., 342° C. and 514°C.

The obtained copolymer (B5) was subjected to GPC measurement under thesame conditions as described in Example B1. The measurement result showsthat the copolymer (B5) had a number average molecular weight (Mn) of16750, a weight average molecular weight (Mw) of 61867, and a molecularweight distribution ratio (Mw/Mn) of 3.7.

Elementary analysis was conducted on the obtained copolymer (B5) underthe same conditions as described in Example A1. The theoretical valuesand the measured values by the elemental analysis are as given below.

measured values: C, 86.49; H, 7.46; N, 0.00; O 6.05.

theoretical values: C, 86.29; H, 7.45; N, 0.00; O 6.25.

The value for oxygen was calculated in the same manner as in Example B1.The result of the measurement was commensurate with the theoreticalvalues predicted in the case where the styrene derivative (A2) wasassumed to be contained in the copolymer by 13%.

The glass transition temperature of the obtained copolymer (B5) wasmeasured in the same manner as described in Example B1. The result ofthe measurement determined the glass transition temperature of thecopolymer (B5) to be 118.5° C.

The volume resistive value of the copolymer (B5) was measured in thesame manner as described in Example B1. The result of the measurementwas that the copolymer (B5) had a volume resistive value of 0.98×10¹⁶Ωcm.

Example B6 Preparation of a Combination of the Formula (A3) Plus Styrenein a Molar Ratio of 5.0:95.0

4.21 g of the styrene derivative (A3) and 30.79 g of styrene weredispersed in 21 ml of DMF, and this solution was heated to 110° C. in anatmosphere of a nitrogen gas stream (50 ml/min). To this solution wasdripped in the course of 18 minutes a mixture liquid of 21 ml of DMF and2.31 g of tert-butyl peroxy isopropyl monocarbonate (PERBUTYL I, aproduct name of NOF CORPORATION). After a reaction was allowed toproceed for four hours at 110° C., the liquid was cooled. The obtainedreaction liquid was dripped into 500 ml of methanol, whereby aprecipitation of rubber-like white substance occurred. After removing asupernatant by decantation, the substance was dissolved in 150 ml oftetrahydrofuran, and the solution was added to 2 liters of methanol tooccasion a precipitation and the precipitate was filtered aside. Then,the substance was dried at 90° C. under a reduced pressure for 20 hours,and 29.56 g of a copolymer (B6) was obtained.

The obtained copolymer (B6) was subjected to an examination by means of¹H-NMR under the same conditions as described in Example B1, and therewere observed no peaks that should, respectively, represent the vinylgroup of the styrene and the styrene derivative (A3) represented by theFormula (A3) as a starting materials before the copolymerizationreaction, whereas broad aromatic proton(s) and alkyl chain(s) wereobserved, and furthermore, a broad hydroxyl group originating from thestyrene derivative (A3) and a broad proton of δ(ppm)=4.97 (—CH₂—O—) wereobserved. From the integrated values of the peaks, it was determinedthat the constituent unit obtained from the styrene derivative (A3) wascontained in the obtained copolymer by 4.68%.

The obtained copolymer (B6) was subjected to FT-IR analysis under thesame conditions as described in Example B1, and the followingobservation was made.

v(cm⁻¹)=3427, 3059, 3026, 2922, 2848, 1941, 1873, 1805, 1741, 1674,1622, 1601, 1583, 1493, 1452, 1371, 1244, 1182, 1151, 1092, 1028, 978,962, 906, 839, 758, 698, 540.

The obtained copolymer (B6) is composed of Unit C, which is aconstituent unit obtained from the Compound Example b1-1 and iscontained in the Formula (5), and Unit B, which is the constituent unitrepresented by the Formula (9).

A measurement was conducted on the obtained copolymer (B6) for TG-DTAunder the same conditions described in Example B1. The measurementresult shows that the heat generation temperatures were 367° C. and 539°C., and the weight loss temperatures were 213° C., 344° C. and 517° C.

The obtained copolymer (B6) was subjected to GPC measurement under thesame conditions as described in Example B1. The measurement result ofthe molecular weight distribution of the copolymer (B6) as measuredunder the above-described conditions showed that the copolymer (B6) hada number average molecular weight (Mn) of 7088, a weight averagemolecular weight (Mw) of 18085, and a molecular weight distributionratio (Mw/Mn) of 2.6.

The glass transition temperature of the obtained copolymer (B6) wasmeasured in the same manner as described in Example B1. The result ofthe measurement determined the glass transition temperature of thecopolymer (B6) to be 105.2° C.

It was also determined that the volume resistive value of the copolymer(B6) was 0.61×10¹⁶ Ωcm.

Example B7 Preparation of a Combination of the Formula (A1) Plus Styrenein a Molar Ratio of 5.0:95.0

8.41 g of the styrene derivative (A1) and 61.60 g of styrene weredispersed in 42 ml of DMF, and this was heated to 110° C. in anatmosphere of a nitrogen gas stream (50 ml/min). To this solution wasdripped in the course of 24 minutes a mixture liquid of 42 ml of DMF and4.62 g of tert-butyl peroxy isopropyl monocarbonate (PERBUTYL I, aproduct name of NOF CORPORATION). After a reaction was allowed toproceed for 4 hours at 110° C., the liquid was cooled. The thus obtainedreaction liquid was added to 300 ml of tetrahydrofuran, and the solutionwas added to 3.5 liters of methanol to occasion a precipitation and theprecipitate was filtered aside. Then, the residue was washed twice with200 ml of methanol and was dried at 90° C. under a reduced pressure for30 hours, and 59.19 g of a copolymer (B7) was obtained.

The obtained copolymer (B7) was examined by means of ¹H-NMR under thesame conditions as described in Example B1, and there were observed nopeaks that should, respectively, represent the vinyl group of thestyrene and the styrene derivative (A1) represented by the Formula (A1)as a starting materials before the copolymerization reaction, whereasbroad aromatic proton(s) and alkyl chain(s) were observed, andfurthermore, a broad hydroxyl group originating from the styrenederivative (A1) and a broad proton in the vicinity of δ(ppm)=4.9(—CH₂—O—) were observed. From the integrated values of the peaks, it wasdetermined that the constituent unit obtained from the styrenederivative (A1) was contained in the obtained copolymer by 4.73%.

The obtained copolymer (B7) was subjected to FT-IR analysis under thesame conditions as described in Example B1, and the followingobservation was made.

v(cm⁻¹)=3433, 3059, 3026, 2922, 2848, 1944, 1873, 1801, 1741, 1678,1616, 1601, 1493, 1452, 1265, 1215, 1155, 1070, 1028, 906, 758, 698,540.

The obtained copolymer (B7) is composed of Unit D, which is aconstituent unit obtained from the Compound Example a1-1 and iscontained in the Formula (5), and Unit B, which is the constituent unitrepresented by the Formula (9).

A measurement was conducted on the obtained copolymer (B7) for TG-DTAunder the same conditions as described in Example B1. The measurementresult shows that the heat generation temperatures were 347° C. and 542°C., and the weight loss temperatures were 329° C., 393° C. and 520° C.

The obtained copolymer (B7) was subjected to GPC measurement under thesame conditions as described in Example B1. The measurement resultshowed that the copolymer (B7) had a number average molecular weight(Mn) of 10118, a weight average molecular weight (Mw) of 48190, and amolecular weight distribution ratio (Mw/Mn) of 4.8.

The glass transition temperature of the obtained copolymer (B7) wasmeasured in the same manner as described in Example B1. The result ofthe measurement determined the glass transition temperature of thecopolymer (B7) to be 104.6° C.

Example B8 Preparation of a Combination of the Formula (A6) Plus Styrenein a Molar Ratio of 5.0:95.0

5.25 g of the styrene derivative (A6) and 29.75 g of styrene weredispersed in 21 ml of DMF, and this was heated to 110° C. in anatmosphere of a nitrogen gas stream (50 ml/min). To this solution wasdripped in the course of 18 minutes a mixture liquid of 21 ml of DMF and2.31 g of tert-butyl peroxy isopropyl monocarbonate (PERBUTYL I, aproduct name of NOF CORPORATION). After a reaction was allowed toproceed for 4 hours at 110° C., the liquid was cooled. The thus obtainedreaction liquid was dripped into 500 ml of methanol, a precipitation ofgreen substance occurred. This precipitate was dissolved in 150 ml oftetrahydrofuran and the solution was added to 1.5 liters of methanol tooccasion a precipitation and the precipitate was filtered aside. Then,the residue was washed twice with sprinkling of 50 ml of methanol, andwas dried at 90° C. under a reduced pressure for 15 hours, and 31.71 gof a copolymer (B8) was obtained.

The obtained copolymer (B8) was examined by means of ¹H-NMR under thesame conditions as described in Example B1, and there were observed nopeaks that should, respectively, represent the vinyl group of thestyrene and the styrene derivative (A6) represented by the Formula (A6)as a starting materials before the copolymerization reaction, whereasbroad aromatic proton(s) and alkyl chain(s) were observed, andfurthermore, a broad hydroxyl group originating from the styrenederivative (A6) and a broad proton in the vicinity of δ(ppm)=5.04(—CH₂—O—) were observed. From the integrated values of the peaks, it wasdetermined that the constituent unit obtained from the styrenederivative (A6) was contained in the obtained copolymer by 4.82%.

The obtained copolymer (B8) was subjected to FT-IR analysis under thesame conditions as described in Example B1, and the followingobservation was made.

v(cm⁻¹)=3427, 3082, 3059, 3026, 2921, 2848, 1940, 1872, 1805, 1741,1678, 1612, 1601, 1583, 1493, 1452, 1371, 12, 38, 1182, 1155, 1095,1070, 1030, 906, 837, 756, 698, 620, 540, 449

The obtained copolymer (B8) is composed of Unit E, which is aconstituent unit obtained from the Compound Example b1-21 and iscontained in the Formula (5), and Unit B, which is the constituent unitrepresented by the Formula (9).

A measurement was conducted on the obtained copolymer (B8) for TG-DTAunder the same conditions described in Example B1. The measurementresult shows that the heat generation temperatures were 347° C. and 540°C., and the weight loss temperatures were 221° C., 324° C. and 513° C.

The obtained copolymer (B8) was subjected to GPC measurement under thesame conditions as described in Example B1. It was confirmed from theresult of the measurement that the copolymer (B8) has a number averagemolecular weight (Mn) of 10220, a weight average molecular weight (Mw)of 38008, and a molecular weight distribution ratio (Mw/Mn) of 3.7.

The glass transition temperature of the obtained copolymer (B8) wasmeasured under the same conditions as described in Example B1. Theresult of the measurement determined the glass transition temperature ofthe copolymer (B8) to be 110.1° C.

Example B9 Preparation of a Combination of the Formula (A2) Plus AcrylicAcid Plus Styrene in a Molar Ratio of 5.0:5.0:90.0

5.03 g of the styrene derivative (A2) and 28.87 g of styrene and 1.11 gof acrylic acid and 1.75 g of 2,2′-azobis(2,4-dimethyl valeronitrile)were dissolved in 21 ml of tetrahydrofuran, and this monomer solutionwas stirred for 2 hours. Aside from this, 21 ml of tetrahydrofuran wasstirred for one hour at 66° C. in an atmosphere of nitrogen gas stream(50 ml/min). To this tetrahydrofuran was dripped the monomer solution inthe course of 37 minutes, followed by 4-hour stirring and then cooling.Thereafter the reaction liquid was dripped into 500 ml of hexane, and ahighly viscous yellow deposit was obtained. The supernatant liquid wasremoved, and the remnant was dried for 48 hours at 70° C. under areduced pressure, and the solid was dissolved in 100 ml of ethylacetate, and this solution was dripped into 1.5 liters of hexane wherebysome white solid material was obtained. This was filtered aside, andwashed twice with 100 ml of hexane, and the residue was dried for 15hours at 90° C. under a reduced pressure, and 18.24 g of a copolymer(B9) was obtained.

The obtained copolymer (B9) was examined by means of ¹H-NMR under thesame conditions as described in Example B1, and there were observed nopeaks that should, respectively, represent the vinyl group of thestyrene and the styrene derivative (A2) represented by the Formula (A2)as a starting materials before the copolymerization reaction, whereasbroad aromatic proton(s) and alkyl chain(s) were observed, andfurthermore, a broad hydroxyl group originating from the styrenederivative (A2) and a broad proton in the vicinity of δ(ppm)=4.92(—CH₂—O—) were observed. From the integrated values of the peaks, it wasdetermined that the constituent unit obtained from the styrenederivative (A2) was contained in the obtained copolymer by 2.31%.

The obtained copolymer (B9) was subjected to FT-IR analysis under thesame conditions as described in Example B1, and the followingobservation was made.

v(cm⁻¹)=3439, 3103, 3082, 3061, 3026, 3001, 2924, 2850, 1944, 1871,1803, 1745, 1686, 1603, 1583, 1512, 1493, 1452, 1437, 1392, 1363, 1311,1275, 1221, 1201, 1182, 1155, 1099, 1030, 1018, 964, 906, 843, 818, 800,758, 698, 540

A measurement was conducted on the obtained copolymer (B9) for TG-DTAunder the same conditions described in Example B1. The measurementresult shows that the heat generation temperatures were 356° C. and 534°C., and the weight loss temperatures were 334° C. and 514° C.

The obtained copolymer (B9) was subjected to GPC measurement under thesame conditions as described in Example B1. The measurement resultshowed that the copolymer (B9) had a number average molecular weight(Mn) of 6976, a weight average molecular weight (Mw) of 11333, and amolecular weight distribution ratio (Mw/Mn) of 1.6.

The glass transition temperature of the obtained copolymer (B9) wasmeasured in the same manner as described in Example B1. The result ofthe measurement determined the glass transition temperature of thecopolymer (B9) to be 107.7° C.

Example B10 Preparation of a Combination of the Formula (A3) PlusAcrylic Acid Plus Styrene in a Molar Ratio of 4.5:15.3:80.2

4.27 g of the styrene derivative (A3) and 29.60 g of styrene and 1.14 gof acrylic acid and 1.75 g of 2,2′-azobis(2,4-dimethyl valeronitrile)were dissolved in 21 ml of tetrahydrofuran, and this monomer solutionwas stirred for 2 hours. Aside from this, 21 ml of tetrahydrofuran wasstirred for one hour at 66° C. in an atmosphere of nitrogen gas stream(50 ml/min). To this tetrahydrofuran was dripped the monomer solution inthe course of 43 minutes, followed by 4-hour stirring and then cooling.Thereafter the reaction liquid was dripped into 500 ml of methanol, anda highly viscous white deposit was obtained. The supernatant liquid wasremoved, and the remnant was dried for 48 hours at 70° C. under areduced pressure, and the solid was dissolved in 100 ml of ethylacetate, and this solution was dripped into 1.5 liters of hexane wherebysome white solid material was obtained. This was filtered aside, andwashed twice with 100 ml of hexane, and the residue was dried for 15hours at 90° C. under a reduced pressure, and 17.73 g of a copolymer(B10) was obtained.

The obtained copolymer (B10) was examined by means of ¹H-NMR under thesame conditions as described in Example B1, and there were observed nopeaks that should, respectively, represent the vinyl group of thestyrene and the styrene derivative (A3) represented by the Formula (A3)as a starting materials before the copolymerization reaction, whereasbroad aromatic proton(s) and alkyl chain(s) were observed, andfurthermore, a broad hydroxyl group originating from the styrenederivative (A3) and a broad proton in the vicinity of δ(ppm)=4.97(—CH₂—O—) were observed. From the integrated values of the peaks, it wasdetermined that the constituent unit obtained from the styrenederivative (A3) was contained in the obtained copolymer by 4.88%.

The obtained copolymer (B10) was subjected to FT-IR analysis under thesame conditions as described in Example B1, and the followingobservation was made.

v(cm⁻¹)=3439, 3103, 3082, 3061, 3026, 3001, 2924, 2850, 1944, 1871,1801, 1743, 1680, 1649, 1624, 1603, 1583, 1493, 1452, 1369, 1244, 1182,1151, 1093, 1072, 1028, 978, 962, 943, 906, 839, 822, 758, 698, 540, 457

The obtained copolymer (B10) is composed of Unit C, which is theconstituent unit obtained from the Compound Example b1-1 and iscontained in the Formula (5), Unit B, which is the constituent unitrepresented by the Formula (9), and Unit F, which is a constituent unitcontained in the Formula (11).

A measurement was conducted on the obtained copolymer (B10) for TG-DTAunder the same conditions described in Example B1. The measurementresult shows that the heat generation temperatures were 352° C. and 538°C., and the weight loss temperatures were 230° C., 337° C. and 517° C.

The obtained copolymer (B10) was subjected to GPC measurement under thesame conditions as described in Example B1. It was confirmed from theresult of the measurement that the copolymer (B10) has a number averagemolecular weight (Mn) of 7612, a weight average molecular weight (Mw) of13037, and a molecular weight distribution ratio (Mw/Mn) of 1.7.

The glass transition temperature of the obtained copolymer (B10) wasmeasured under the same conditions as described in Example B1. Theresult of the measurement determined the glass transition temperature ofthe copolymer (B10) to be 106.6° C.

Example B11 Preparation of a Combination of the Formula (A5) PlusStyrene in a Molar Ratio of 4.2:95.8

4.21 g of the styrene derivative (A5) and 30.80 g of styrene weredispersed in 21 ml of toluene, and this was heated to 110° C. in anatmosphere with nitrogen gas stream (50 ml/min). To this solution wasdripped a mixture solution of 21 ml of toluene and 2.31 g of tert-butylperoxy isopropyl monocarbonate (PERBUTYL I, a product name of NOFCORPORATION) in the course of 21 minutes. A consequent reaction wasfurther allowed to proceed for 4 hours at 110° C., and was then cooled.Thereafter, the reaction liquid was dripped into 500 ml of methanol, anda viscous pale brown substance precipitated. The supernatant methanolwas removed, and the deposit was dissolved in 150 ml of tetrahydrofuran,and this solution was added to 2.0 liters of methanol and aprecipitation occurred, which was then filtered aside. It was washedtwice with sprinkling of 200 ml of methanol, and the residue was driedfor 10 hours at 90° C. under a reduced pressure, and 32.40 g of a whitecopolymer (B11) was obtained.

The obtained copolymer (B11) was examined by means of ¹H-NMR under thesame conditions as described in Example B1, and there were observed nopeaks that should, respectively, represent the vinyl group of thestyrene and the styrene derivative (A5) represented by the Formula (A5)as a starting materials before the copolymerization reaction, whereasbroad aromatic proton(s) and alkyl chain(s) were observed, andfurthermore, a broad hydroxyl group originating from the styrenederivative (A5) and a broad proton in the vicinity of δ(ppm)=5.09(—CH₂—O—) were observed. From the integrated values of the peaks, it wasdetermined that the constituent unit obtained from the styrenederivative (A5) was contained in the obtained copolymer by 3.27%.

The obtained copolymer (B11) was subjected to FT-IR analysis under thesame conditions as described in Example B1, and the followingobservation was made.

v(cm⁻¹)=3425, 3082, 3059, 3026, 2922, 2848, 1940, 1805, 1741, 1687,1681, 1601, 1583, 1493, 1452, 1365, 1273, 1232, 1203, 1180, 1153, 1107,1028, 906, 841, 823, 796, 756, 698, 540.

A measurement was conducted on the obtained copolymer (B11) for TG-DTAunder the same conditions described in Example B1. The measurementresult shows that the heat generation temperature was 539° C., and theweight loss temperatures were 232° C. and 337° C., 514° C.

The obtained copolymer (B11) was subjected to GPC measurement under thesame conditions as described in Example B1. It was confirmed from theresult of the measurement that the copolymer (B11) has a number averagemolecular weight (Mn) of 10371, a weight average molecular weight (Mw)of 28805, and a molecular weight distribution ratio (Mw/Mn) of 2.8.

The glass transition temperature of the obtained copolymer (B11) wasmeasured in the same manner as described in Example B1. The result ofthe measurement determined the glass transition temperature of thecopolymer (B11) to be 99.83° C.

Example B12 Preparation of a Combination of the Formula (A9) PlusStyrene in a Molar Ratio of 5.0:95.0

4.21 g of the styrene derivative (A9) and 30.80 g of styrene weredissolved in 21 ml of toluene, and this was heated to 110° C. in anatmosphere with nitrogen gas stream (50 ml/min). To this solution wasdripped a mixture solution of 21 ml of toluene and 2.31 g of tert-butylperoxy isopropyl monocarbonate (PERBUTYL I, a product name of NOFCORPORATION) in the course of 20 minutes. A consequent reaction wasfurther allowed to proceed for 4 hours at 110° C., and was then cooled.Thereafter, the reaction liquid was dripped into 500 ml of methanol, anda viscous pale brown substance precipitated. The supernatant methanolwas removed, and the deposit was dissolved in 150 ml of tetrahydrofuran,and this solution was added to 2.0 liters of methanol and aprecipitation occurred, which was then filtered aside. It was washedtwice with sprinkling of 200 ml of methanol, and the residue was driedfor 10 hours at 90° C. under a reduced pressure, and 32.87 g of a whitecopolymer (B12) was obtained.

The obtained copolymer (B12) was examined by means of ¹H-NMR under thesame conditions as described in Example B1, and there were observed nopeaks that should, respectively, represent the vinyl group of thestyrene and the styrene derivative (A9) represented by the Formula (A9)as a starting materials before the copolymerization reaction, whereasbroad aromatic proton(s) and alkyl chain(s) were observed, andfurthermore, a broad hydroxyl group originating from the styrenederivative (A9) and a broad proton in the vicinity of δ(ppm)=4.97 and4.82 (—CH₂—O—) were observed. From the integrated values of the peaks,it was determined that the constituent unit obtained from the styrenederivative (A9) was contained in the obtained copolymer by 4.83%.

The obtained copolymer (B12) was subjected to FT-IR analysis under thesame conditions as described in Example B1, and the followingobservation was made.

v(cm⁻¹)=3435, 3082, 3059, 3026, 2922, 2848, 1942, 1873, 1803, 1741,1678, 1651, 1622, 1601, 1583, 1493, 1452, 1373, 1244, 1182, 1151, 1130,1093, 1081, 1028, 978, 962, 906, 839, 756, 698, 540, 455

The obtained copolymer (B12) is composed of Unit C, which is theconstituent unit obtained from the Compound Example b1-1 and iscontained in the Formula (5), Unit G, which is a constituent unitobtained from the Compound Example b2-1 and is contained in the Formula(5), and Unit B, which is the constituent unit represented by theFormula (9).

A measurement was conducted on the obtained copolymer (B12) for TG-DTAunder the same conditions described in Example B1. The measurementresult is shown in FIG. 20. It was observed that the heat generationtemperatures were 405° C. and 536° C., and the weight loss temperatureswere 342° C. and 510° C.

The obtained copolymer (B12) was subjected to GPC measurement under thesame conditions as described in Example B1. It was confirmed from theresult of the measurement that the copolymer (B12) has a number averagemolecular weight (Mn) of 11905, a weight average molecular weight (Mw)of 44906, and a molecular weight distribution ratio (Mw/Mn) of 3.8.

The glass transition temperature of the obtained copolymer (B12) wasmeasured in the same manner as described in Example B1. The result ofthe measurement determined the glass transition temperature of thecopolymer (B12) to be 100.7° C.

Example B13 Preparation of a Combination of the Formula (A8) PlusStyrene in a Molar Ratio of 5.0:95.0

4.21 g of the styrene derivative (A8) and 30.80 g of styrene weredissolved in 21 ml of toluene, and this was heated to 110° C. in anatmosphere with nitrogen gas stream (50 ml/min). To this solution wasdripped a mixture solution of 21 ml of toluene and 2.31 g of tert-butylperoxy isopropyl monocarbonate (PERBUTYL I, a product name of NOFCORPORATION) in the course of 19 minutes. A consequent reaction wasfurther allowed to proceed for 4 hours at 110° C., and was then cooled.Thereafter, the reaction liquid was dripped into 500 ml of methanol, anda viscous pale brown substance precipitated. The supernatant methanolwas removed, and the deposit was dissolved in 150 ml of tetrahydrofuran,and this solution was added to 2.0 liters of methanol and aprecipitation occurred. This was then filtered aside, and was washedtwice with sprinkling of 200 ml of methanol, and the residue was driedfor 10 hours at 90° C. under a reduced pressure, and 32.26 g of a palebrown copolymer (B13) was obtained.

The obtained copolymer (B13) was examined by means of ¹H-NMR under thesame conditions as described in Example B1, and there were observed nopeaks that should, respectively, represent the vinyl group of thestyrene and the styrene derivative (A8) represented by the Formula (A8)as a starting materials before the copolymerization reaction, whereasbroad aromatic proton(s) and alkyl chain(s) were observed, andfurthermore, a broad hydroxyl group originating from the styrenederivative (A8) and a broad proton in the vicinity of δ(ppm)=5.07(—CH₂—O—) were observed. From the integrated values of the peaks, it wasdetermined that the constituent unit obtained from the styrenederivative (A8) was contained in the obtained copolymer by 4.21%.

The obtained copolymer (B13) was subjected to FT-IR analysis under thesame conditions as described in Example B1, and the followingobservation was made.

v(cm⁻¹)=3427, 3082, 3059, 3026, 2922, 2848, 1942, 1867, 1803, 1741,1684, 1660, 1601, 1583, 1493, 1452, 1373, 1257, 1234, 1180, 1153, 1140,1070, 1028, 906, 837, 820, 754, 698, 621, 540.

A measurement was conducted on the obtained copolymer (B13) for TG-DTAunder the same conditions described in Example B1. The measurementresult is shown in FIG. 21. It was observed that the heat generationtemperature was 539° C., and the weight loss temperatures were 341° C.and 515° C.

The obtained copolymer (B13) was subjected to GPC measurement under thesame conditions as described in Example B1. It was confirmed from theresult of the measurement that the copolymer (B13) has a number averagemolecular weight (Mn) of 10442, a weight average molecular weight (Mw)of 52933, and a molecular weight distribution ratio (Mw/Mn) of 5.1.

The glass transition temperature of the obtained copolymer (B13) wasmeasured in the same manner as described in Example B1. The result ofthe measurement determined the glass transition temperature of thecopolymer (B13) to be 99.25° C.

Example B14 Preparation of a Combination of the Formula (A2) PlusStyrene in a Molar Ratio of 0.1:99.9

0.11 g of the styrene derivative (A2) and 34.89 g of styrene weredispersed in 21 ml of toluene, and this was heated to 110° C. in anatmosphere with nitrogen gas stream (50 ml/min). To this solution wasdripped a mixture solution of 21 ml of toluene and 2.31 g of tert-butylperoxy isopropyl monocarbonate (PERBUTYL I, a product name of NOFCORPORATION) in the course of 21 minutes. A consequent reaction wasfurther allowed to proceed for 4 hours at 110° C., and was then cooled.Thereafter, the reaction liquid was dripped into 500 ml of methanol, anda viscous white substance precipitated. The supernatant liquid wasremoved, and the deposit was dissolved in 150 ml of tetrahydrofuran, andthis solution was added to 2.0 liters of methanol and a reprecipitationoccurred. This was then filtered aside, and was washed twice withsprinkling of 200 ml of methanol, and the residue was dried for 30 hoursat 80° C., and 32.18 g of a copolymer (B14) was obtained.

The obtained copolymer (B14) was examined by means of ¹H-NMR under thesame conditions as described in Example B1, and there were observed nopeaks that should, respectively, represent the vinyl group of thestyrene and the styrene derivative (A2) represented by the Formula (A2)as a starting materials before the copolymerization reaction.

The obtained copolymer (B14) was subjected to FT-IR analysis under thesame conditions as described in Example B1, and the followingobservation was made.

v(cm⁻¹)=3439, 3103, 3082, 3061, 3026, 3001, 2922, 2848, 1942, 1871,1801, 1741, 1601, 1583, 1541, 1493, 1452, 1373, 1329, 1311, 1263, 1182,1155, 1068, 1028, 1003, 980, 964, 943, 906, 841, 756, 698, 621, 538.

A measurement was conducted on the obtained copolymer (B14) for TG-DTAunder the same conditions described in Example B1. The measurementresult indicated that the weight loss temperatures were 316° C. and 517°C.

The obtained copolymer (B14) was subjected to GPC measurement under thesame conditions as described in Example B1. It was confirmed from theresult of the measurement that the copolymer (B14) has a number averagemolecular weight (Mn) of 7968, a weight average molecular weight (Mw) of20110, and a molecular weight distribution ratio (Mw/Mn) of 2.5.

The glass transition temperature of the obtained copolymer (B14) wasmeasured in the same manner as described in Example B1. The result ofthe measurement determined the glass transition temperature of thecopolymer (B14) to be 89.05° C.

Example B15 Preparation of a Combination of the Formula (A12) PlusStyrene in a Molar Ratio of 5.0:95.0

5.67 g of the styrene derivative (A12) and 29.93 g of styrene weredispersed in 21 ml of toluene, and this was heated to 110° C. in anatmosphere with nitrogen gas stream (50 ml/min). To this solution wasdripped a mixture solution of 21 ml of toluene and 2.31 g of tert-butylperoxy isopropyl monocarbonate (PERBUTYL I, a product name of NOFCORPORATION) in the course of 28 minutes. A consequent reaction wasfurther allowed to proceed for 4 hours at 110° C., and was then cooled.Thereafter, the reaction liquid was dripped into one liter of methanol,and a highly viscous white substance precipitated. The supernatantliquid was removed, and the deposit was dissolved in 150 ml oftetrahydrofuran, and this solution was dripped into 2 liters of methanolfor refinement by reprecipitation. This was then filtered aside, and waswashed twice with 200 ml of methanol, and the residue was dried for 24hours at 60° C., and 27.3 g of a copolymer (B15) was obtained.

The obtained copolymer (B15) was examined by means of ¹H-NMR under thesame conditions as described in Example B1, and there were observed nopeaks that should, respectively, represent the vinyl group of thestyrene and the styrene derivative (A12) represented by the Formula(A12) as a starting materials before the copolymerization reaction,whereas broad aromatic proton(s) and alkyl chain(s) were observed, andfurthermore, a broad hydroxyl group originating from the styrenederivative (A12) and a broad proton in the vicinity of δ(ppm)=5.10(—CH₂—O—) were observed. From the integrated values of the peaks, it wasdetermined that the constituent unit obtained from the styrenederivative (A12) was contained in the obtained copolymer by 3.99%.

The obtained copolymer (B15) was subjected to FT-IR analysis under thesame conditions as described in Example B1, and the followingobservation was made.

v(cm⁻¹)=3460, 3078, 3069, 3033, 2966, 2930, 2922, 2875, 2859, 2733,1944, 1887, 1800, 1715, 1678, 1611, 1470, 1464, 1458, 1437, 1373, 1322,1245, 1226, 1193, 1147, 1134, 1123, 1069, 1040, 976, 943, 911, 841, 801,766, 701, 544.

A measurement was conducted on the obtained copolymer (B15) for TG-DTAunder the same conditions described in Example B1. The measurementresult indicated that the heat generation temperatures were 329° C. and529° C., and the weight loss temperatures were 335° C. and 510° C.

The obtained copolymer (B15) was subjected to GPC measurement under thesame conditions as described in Example B1. It was confirmed from theresult of the measurement that the copolymer (B15) has a number averagemolecular weight (Mn) of 12071, a weight average molecular weight (Mw)of 52749, and a molecular weight distribution ratio (Mw/Mn) of 4.4.

The glass transition temperature of the obtained copolymer (B15) wasmeasured in the same manner as described in Example B1. The result ofthe measurement determined the glass transition temperature of thecopolymer (B15) to be 89.5° C.

The volume resistive value of the copolymer (B15) was 2.7×10¹⁶ Ωcm.

Example B16 Preparation of a Combination of the Formula (A2) Plus2-Ethylhexyl Acrylate Plus Styrene in a Molar Ratio of 5.0:5.0:90.0

4.79 g of the styrene derivative (A2) and 27.51 g of styrene and 2.70 gof 2-ethylhexyl acrylate were dissolved in a mixture solution of 1.1 gof methanol and 4.4 g of tetrahydrofuran, and to this was added 1.05 gof 2,2′-azobis(2,4-dimethyl valeronitrile). This solution was drippedinto a mixture consisting of 16.4 g of methanol and 70 g oftetrahydrofuran, which mixture had been heated to 65° C. in anatmosphere with nitrogen gas stream (50 ml/min), and this dripping wascompleted in the course of 24 minutes. A consequent reaction was furtherallowed to proceed for 6 hours at 65° C., and was then cooled.Thereafter, the reaction liquid was dripped into 2 liters of methanol,and a white solid substance precipitated. After filtering, the residuewas washed with methanol and the same was dried for 10 hours at 90° C.under a reduced pressure, and 10.72 g of a white copolymer (B16) wasobtained.

The obtained copolymer (B16) was examined by means of ¹H-NMR under thesame conditions as described in Example B1, and there were observed nopeaks that should, respectively, represent the vinyl group of thestyrene and the styrene derivative (A2) represented by the Formula (A2)as a starting materials before the copolymerization reaction, whereasbroad aromatic proton(s) and alkyl chain(s) were observed, andfurthermore, a broad hydroxyl group originating from the styrenederivative (A2) and a broad proton in the vicinity of δ(ppm)=4.92(—CH₂—O—) were observed. From the integrated values of the peaks, it wasdetermined that the constituent unit obtained from the styrenederivative (A2) was contained in the obtained copolymer by 5.01%, andthat the constituent unit obtained from the 2-ethylhexyl acrylate wascontained in the same by 5.80%.

The obtained copolymer (B16) was subjected to FT-IR analysis under thesame conditions as described in Example B1, and the followingobservation was made.

v(cm⁻¹)=3435, 3082, 3061, 3026, 2924, 2872, 2854, 1940, 1874, 1865,1728, 1687, 1678, 1659, 1651, 1643, 1603, 1583, 1493, 1452, 1439, 1392,1377, 1309, 1275, 1198, 1180, 1155, 1101, 1030, 964, 906, 843, 800, 758,698, 540.

A measurement was conducted on the obtained copolymer (B16) for TG-DTAunder the same conditions described in Example B1. The measurementresult indicated that the heat generation temperature was 541° C., andthe weight loss temperatures were 350° C. and 513° C.

The obtained copolymer (B16) was subjected to GPC measurement under thesame conditions as described in Example B1. It was confirmed from theresult of the measurement that the copolymer (B16) has a number averagemolecular weight (Mn) of 6720, a weight average molecular weight (Mw) of10466, and a molecular weight distribution ratio (Mw/Mn) of 1.6.

The glass transition temperature of the obtained copolymer (B16) wasmeasured in the same manner as described in Example B1. The result ofthe measurement determined the glass transition temperature of thecopolymer (B16) to be 84.0° C.

Example B17 Preparation of a Combination of the Formula (A2) Plusn-Butyl Acrylate Plus Styrene in a Molar Ratio of 5.0:5.0:90.0

4.90 g of the styrene derivative (A2) and 28.17 g of styrene and 1.93 gof n-butyl acrylate were dissolved in a mixture solution of 3.35 g ofmethanol and 2.50 g of toluene and 4.15 g of methyl ethyl ketone, and tothis was added 1.75 g of dimethyl-2,2′-azobis(2-methyl propionate). Thissolution was dripped into a mixture consisting of 20.10 g of methanoland 17.15 g of toluene and 24.90 g of methyl ethyl ketone, which mixturehad been heated to 65° C. in an atmosphere with nitrogen gas stream (50ml/min), and this dripping was completed in the course of 25 minutes. Aconsequent reaction was further allowed to proceed for 6 hours at 65°C., and was then cooled. Thereafter, the reaction liquid was drippedinto 2 liters of methanol, and a white solid substance precipitated.After filtering, the residue was dissolved in 150 ml of tetrahydrofuran.This solution was added to 2 liters of methanol and obtained aprecipitate and it was filtered aside. This was washed by beingsprinkled twice with 200 ml of methanol, and the residue was dried for15 hours at 70° C. under a reduced pressure, and 8.41 g of whitecopolymer (B17) was obtained.

The obtained copolymer (B17) was examined by means of ¹H-NMR under thesame conditions as described in Example B1, and there were observed nopeaks that should, respectively, represent the vinyl group of thestyrene and the styrene derivative (A2) represented by the Formula (A2)as a starting materials before the copolymerization reaction, whereasbroad aromatic proton(s) and alkyl chain(s) were observed, andfurthermore, a broad hydroxyl group originating from the styrenederivative (A2) and a broad proton in the vicinity of δ(ppm)=4.93(—CH₂—O—) were observed. From the integrated values of the peaks, it wasdetermined that the constituent unit obtained from the styrenederivative (A2) was contained in the obtained copolymer by 6.35%, andthat the constituent unit obtained from the 2-ethylhexyl acrylate wascontained in the same by 6.09%.

The obtained copolymer (B17) was subjected to FT-IR analysis under thesame conditions as described in Example B1, and the followingobservation was made.

v(cm⁻¹)=3429, 3082, 3061, 3026, 3001, 2924, 2850, 1942, 1873, 1799,1730, 1682, 1603, 1583, 1493, 1452, 1437, 1392, 1363, 1309, 1273, 1200,1180, 1155, 1030, 906, 843, 800, 758, 698, 540.

The obtained copolymer (B17) is composed of Unit A, which is theconstituent unit obtained from the Compound Example a1-2 and iscontained in the Formula (5), and Unit B, which is the constituent unitrepresented by the Formula (9), and Unit H, which is a constituent unitincluded in the Formula (11).

A measurement was conducted on the obtained copolymer (B17) for TG-DTAunder the same conditions described in Example B1. The measurementresult indicated that the heat generation temperatures were 356° C. and532° C., and the weight loss temperatures were 246° C., 341° C. and 512°C.

The obtained copolymer (B17) was subjected to GPC measurement under thesame conditions as described in Example B1. It was confirmed from theresult of the measurement that the copolymer (B17) has a number averagemolecular weight (Mn) of 10750, a weight average molecular weight (Mw)of 16359, and a molecular weight distribution ratio (Mw/Mn) of 1.5.

The glass transition temperature of the obtained copolymer (B17) wasmeasured in the same manner as described in Example B1. The result ofthe measurement determined the glass transition temperature of thecopolymer (B17) to be 95.5° C.

Example B18 Preparation of a Combination of the Formula (A2) Plus MethylMethacrylate Plus n-Butyl Acrylate Plus Styrene in a Molar Ratio of5.0:5.0:5.0:85.0

4.94 g of the styrene derivative (A2) and 26.81 g of styrene and 1.30 gof methyl methacrylate and 1.94 g of n-butyl acrylate were dissolved in21 ml of toluene, and this was heated to 110° C. in an atmosphere withnitrogen gas stream (50 ml/min). This solution was dripped in asolution, which had been prepared by dissolving 2.31 g of tert-butylperoxy isopropyl monocarbonate (PERBUTYL I, a product name of NOFCORPORATION) in 21 mil of toluene, and this dripping was completed inthe course of 17 minutes. A consequent reaction was further allowed toproceed for 4 hours at 110° C., and was then cooled. Thereafter, thereaction liquid was dripped into 2 liters of methanol, and a highlyviscous white solid substance precipitated. The supernatant methanol wasremoved, and the remnant was dissolved in 150 ml of tetrahydrofuran, andthis solution was added to 2 liters of methanol and obtained aprecipitate, and after removing the supernatant liquid, it was filteredaside. This was washed by being sprinkled twice with 200 ml of methanol,and the residue was dried for 20 hours at 90° C. under a reducedpressure, and 28.32 g of a white copolymer (B18) was obtained.

The obtained copolymer (B18) was examined by means of ¹H-NMR under thesame conditions as described in Example B1, and there were observed nopeaks that should, respectively, represent the vinyl group of thestyrene and the styrene derivative (A2) represented by the Formula (A2)as a starting materials before the copolymerization reaction, whereasbroad aromatic proton(s) and alkyl chain(s) were observed, andfurthermore, a broad hydroxyl group originating from the styrenederivative (A2) and a broad proton in the vicinity of δ(ppm)=4.92(—CH₂—O—) were observed. From the integrated values of the peaks, it wasdetermined that the constituent unit obtained from the styrenederivative (A2) was contained in the obtained copolymer by 5.03%, andthat the constituent unit obtained from the methyl methacrylate wascontained in the same by 5.18%, and that the constituent unit obtainedfrom the n-butyl acrylate was contained in the same by 3.37%.

The obtained copolymer (B18) was subjected to FT-IR analysis under thesame conditions as described in Example B1, and the followingobservation was made.

v(cm⁻¹)=3437, 3082, 3061, 3026, 3001, 2924, 2850, 1940, 1873, 1805,1730, 1687, 1680, 1601, 1493, 1452, 1435, 1392, 1362, 1265, 1219, 1201,1180, 1155, 1101, 1064, 1030, 964, 906, 840, 800, 758, 698, 540.

The obtained copolymer (B18) is composed of Unit A, which is theconstituent unit obtained from the Compound Example a1-2 and iscontained in the Formula (5), and Unit B, which is the constituent unitrepresented by the Formula (9), Unit I, which is the constituent unitcontained in the Formula (11), and Unit H, which is the constituent unitcontained in the Formula (11).

A measurement was conducted on the obtained copolymer (B18) for TG-DTAunder the same conditions described in Example B1. The result of themeasurement for TG-DTA is shown in FIG. 22. The measurement resultindicated that the heat generation temperatures were 348° C. and 528°C., and the weight loss temperatures were 334° C. and 511° C.

The obtained copolymer (B18) was subjected to GPC measurement under thesame conditions as described in Example B1. It was confirmed from theresult of the measurement that the copolymer (B18) has a number averagemolecular weight (Mn) of 18602, a weight average molecular weight (Mw)of 72809, and a molecular weight distribution ratio (Mw/Mn) of 3.9.

The glass transition temperature of the obtained copolymer (B18) wasmeasured in the same manner as described in Example B1. The result ofthe measurement determined the glass transition temperature of thecopolymer (B18) to be 103.8° C.

Example B19 Preparation of a Combination of the Formula (A7) PlusStyrene in a Molar Ratio of 5.0:95.0

4.21 g of the styrene derivative (A7) and 30.80 g of styrene weredissolved in 21 ml of toluene, and heated to 110° C. in an atmospherewith nitrogen gas stream (50 ml/min). To this solution was dripped amixture of 21 ml of toluene and 2.31 g of tert-butyl peroxy isopropylmonocarbonate (PERBUTYL I, a product name of NOF CORPORATION) and thisdripping was completed in the course of 19 minutes. A consequentreaction was further allowed to proceed for 4 hours at 110° C., and wasthen cooled. Thereafter, the reaction liquid was dripped into 500 ml ofmethanol, and a viscous white substance precipitated. After thesupernatant methanol was removed, the precipitate was dissolved in 150ml of tetrahydrofuran, and this solution was added to 2.0 liters ofmethanol and obtained a precipitate. This was filtered aside, and waswashed by being sprinkled twice with 200 ml of methanol, and the residuewas dried for 10 hours at 90° C. under a reduced pressure, and 29.81 gof white copolymer (B19) was obtained.

The obtained copolymer (B19) was examined by means of ¹H-NMR under thesame conditions as described in Example B1, and there were observed nopeaks that should, respectively, represent the vinyl group of thestyrene and the styrene derivative (A7) represented by the Formula (A7)as a starting materials before the copolymerization reaction, whereasbroad aromatic proton(s) and alkyl chain(s) were observed, andfurthermore, a broad hydroxyl group originating from the styrenederivative (A7) and a broad proton in the vicinity of δ(ppm)=4.95 wereobserved. From the integrated values of the peaks, it was determinedthat the constituent unit obtained from the styrene derivative (A7) wascontained in the obtained copolymer by 4.32%.

The obtained copolymer (B19) was subjected to FT-IR analysis under thesame conditions as described in Example B1, and the followingobservation was made.

v(cm⁻¹)=3435, 3455, 3081, 3061, 3025, 2922, 2850, 1941, 1866, 1779,1741, 1673, 1600, 1492, 1452, 1361, 1265, 1201, 1155, 1029, 906, 756,698, 540.

The obtained copolymer (B19) was subjected to GPC measurement under thesame conditions as described in Example B1. It was confirmed from theresult of the measurement that the copolymer (B19) has a number averagemolecular weight (Mn) of 15388, a weight average molecular weight (Mw)of 58200, and a molecular weight distribution ratio (Mw/Mn) of 3.8.

The glass transition temperature of the obtained copolymer (B19) wasmeasured in the same manner as described in Example B1. The result ofthe measurement determined the glass transition temperature of thecopolymer (B19) to be 83.2° C.

Example B20 Preparation of a Combination of the Formula (A10) PlusStyrene in a Molar Ratio of 5.0:95.0

4.21 g of the styrene derivative (A10) and 30.79 g of styrene weredispersed in 21 ml of toluene, and this was heated to 110° C. in anatmosphere of a nitrogen gas stream (50 ml/min). To this solution wasdripped in the course of 22 minutes a mixture liquid of 21 ml of DMF and2.31 g of tert-butyl peroxy isopropyl monocarbonate (PERBUTYL I, aproduct name of NOF CORPORATION). A consequent reaction was furtherallowed to proceed for 4 hours at 110° C., and was then cooled.Thereafter, the reaction liquid was dripped into 500 ml of methanol, anda white substance precipitated, and was filtered aside. The whiteprecipitate was dissolved in 150 ml of tetrahydrofuran, and thissolution was dripped into 2 liters of methanol and a white deposit wasobtained. This was filtered aside, and was washed twice with 200 ml ofmethanol, and the residue was dried for 15 hours at 90° C. under areduced pressure, and 29.37 g of a copolymer (B20) was obtained.

The obtained copolymer (B20) was examined by means of ¹H-NMR under thesame conditions as described in Example B1, and there were observed nopeaks that should, respectively, represent the vinyl group of thestyrene and the styrene derivative (A10) represented by the Formula(A10) as a starting materials before the copolymerization reaction,whereas broad aromatic proton(s) and alkyl chain(s) were observed, andfurthermore, a broad hydroxyl group originating from the styrenederivative (A10) and a broad proton at δ(ppm)=5.03 (—CH₂—O—) wereobserved. From the integrated values of the peaks, it was determinedthat the constituent unit obtained from the styrene derivative (A10) wascontained in the obtained copolymer by 3.84%.

The obtained copolymer (B20) was subjected to FT-IR analysis under thesame conditions as described in Example B1, and the followingobservation was made.

v(cm⁻¹)=3523, 3446, 3103, 3082, 3059, 3026, 3001, 2922, 2848, 1942,1873, 1803, 1732, 1686, 1616, 1601, 1583, 1510, 1493, 1452, 1410, 1375,1354, 1277, 1217, 1198, 1182, 1155, 1132, 1119, 1093, 1070, 1028, 1003,964, 941, 906, 868, 841, 820, 758, 698, 623, 540, 432.

A measurement was conducted on the obtained copolymer (B20) for TG-DTAunder the same conditions described in Example B1. The measurementresult indicated that the heat generation temperatures were 333° C.,410° C. and 537° C., and the weight loss temperatures were 335° C., 395°C. and 515° C.

The obtained copolymer (B20) was subjected to GPC measurement under thesame conditions as described in Example B1. It was confirmed from theresult of the measurement that the copolymer (B20) has a number averagemolecular weight (Mn) of 9371, a weight average molecular weight (Mw) of25826, and a molecular weight distribution ratio (Mw/Mn) of 2.8.

The glass transition temperature of the obtained copolymer (B20) wasmeasured in the same manner as described in Example B1. The result ofthe measurement determined the glass transition temperature of thecopolymer (B20) to be 108.8° C.

Example B21 Preparation of a Combination of the Formula (A2) PlusStyrene in a Molar Ratio of 5.0:95.0

4.96 g of the styrene derivative (A2) and 30.04 g of styrene weredispersed in 21 ml of toluene and heated to 110° C. in an atmospherewith nitrogen gas stream (50 ml/min). Into this solution was dripped amixture liquid of 21 ml of toluene and 2.31 g of tert-butyl peroxyisopropyl monocarbonate (PERBUTYL I, a product name of NOF CORPORATION),and this dripping took 21 minutes. A consequent reaction was furtherallowed to proceed for 2.5 hours at 110° C. with vigorous stirring, andwas then cooled. Thereafter, the reaction liquid was dripped into 500 mlof methanol, and a highly viscous white deposit separated. Afterremoving the supernatant liquid, the deposit was dissolved in 150 ml oftetrahydrofuran, and this solution was dripped into 2 liters of methanolto thereby effect reprecipitation refinement. The deposit was filteredaside, and was washed twice with 200 ml of methanol, and the residue wasdried for 15 hours at 90° C. under a reduced pressure, and 32.47 g of acopolymer (B21) was obtained.

The obtained copolymer (B21) was examined by means of ¹H-NMR under thesame conditions as described in Example B1, and there were observed nopeaks that should, respectively, represent the vinyl group of thestyrene and the styrene derivative (A2) represented by the Formula (A2)as a starting materials before the copolymerization reaction, whereasbroad aromatic proton(s) and alkyl chain(s) were observed, andfurthermore, a broad hydroxyl group originating from the styrenederivative (A2) and a broad proton at δ(ppm)=5.00 (—CH₂—O—) wereobserved. From the integrated values of the peaks, it was determinedthat the constituent unit obtained from the styrene derivative (A2) wascontained in the obtained copolymer by 3.67%.

The obtained copolymer (B21) was subjected to FT-IR analysis under thesame conditions as described in Example B1, and the followingobservation was made.

v(cm⁻¹)=3491, 3103, 3082, 3061, 3026, 3001, 2922, 2848, 1942, 1871,1803, 1726, 1684, 1639, 1601, 1583, 1547, 1512, 1493, 1452, 1431, 1363,1348, 1300, 1255, 1221, 1180, 1153, 1105, 1066, 1043, 1028, 1018, 980,964, 943, 906, 843, 822, 758, 698, 669, 619, 607, 596, 540, 417.

A measurement was conducted on the obtained copolymer (B21) for TG-DTAunder the same conditions described in Example B1. The measurementresult indicated that the heat generation temperatures were 351° C.,409° C. and 536° C., and the weight loss temperatures were 330° C., 389°C. and 515° C.

The obtained copolymer (B21) was subjected to GPC measurement under thesame conditions as described in Example B1. It was confirmed from theresult of the measurement that the copolymer (B21) has a number averagemolecular weight (Mn) of 16557, a weight average molecular weight (Mw)of 100309, and a molecular weight distribution ratio (Mw/Mn) of 6.1.

The glass transition temperature of the obtained copolymer (B21) wasmeasured in the same manner as described in Example B1. The result ofthe measurement determined the glass transition temperature of thecopolymer (B21) to be 109.0° C.

Example B22 Preparation of a Combination of the Formula (A13) PlusStyrene in a Molar Ratio of 5.0:95.0

4.21 g of the styrene derivative (A13) and 30.79 g of styrene weredispersed in 21 ml of DMF and heated to 110° C. in an atmosphere withnitrogen gas stream (50 ml/min). Into this solution was dripped amixture liquid of 21 ml of DMF and 2.31 g of tert-butyl peroxy isopropylmonocarbonate (PERBUTYL I, a product name of NOF CORPORATION), and thisdripping took 18 minutes. A consequent reaction was further allowed toproceed for 4 hours at 110° C., and was then cooled. Thereafter, thereaction liquid was dripped into 500 ml of methanol, and a rubber-likewhite deposit separated. After removing the supernatant liquid bydecantation, the deposit was dissolved in 150 ml of tetrahydrofuran.This solution was dripped into 2 liters of methanol, whereby aprecipitate occurred, and it was filtered aside and was dried for 20hours at 90° C. under a reduced pressure, and 27.21 g of a copolymer(B22) was obtained.

The obtained copolymer (B22) was examined by means of ¹H-NMR under thesame conditions as described in Example B1, and there were observed nopeaks that should, respectively, represent the vinyl group of thestyrene and the styrene derivative (A13) represented by the Formula(A13) as a starting materials before the copolymerization reaction,whereas broad aromatic proton(s) and alkyl chain(s) were observed, andfurthermore, a broad hydroxyl group originating from the styrenederivative (A13) and a broad proton at δ(ppm)=5.02 (—CH₂—O—) wereobserved. From the integrated values of the peaks, it was determinedthat the constituent unit obtained from the styrene derivative (A13) wascontained in the obtained copolymer by 4.77%.

The obtained copolymer (B22) was subjected to FT-IR analysis under thesame conditions as described in Example B1, and the followingobservation was made.

v(cm⁻¹)=3522, 3062, 3028, 2921, 2847, 1945, 1880, 1797, 1737, 1670,1619, 1600, 1588, 1489, 1466, 1367, 1250, 1179, 1149, 1100, 1023, 975,966, 902, 843, 760, 701, 537.

The obtained copolymer (B22) is composed of Unit A, which is theconstituent unit obtained from the Compound Example a1-2 and iscontained in the Formula (5), Unit J, which is a constituent unitobtained from the Compound Example a3-2 and is contained in the Formula(5), and Unit B, which is the constituent unit represented by theFormula (9).

A measurement was conducted on the obtained copolymer (B22) for TG-DTAunder the same conditions described in Example B1. The measurementresult indicated that the heat generation temperatures were 376° C. and541° C., and the weight loss temperatures were 222° C., 356° C. and 528°C.

The obtained copolymer (B22) was subjected to GPC measurement under thesame conditions as described in Example B1. It was confirmed from theresult of the molecular weight distribution measurement conducted undersaid conditions on the copolymer (B22) that the copolymer (B22) has anumber average molecular weight (Mn) of 8327, a weight average molecularweight (Mw) of 12245, and a molecular weight distribution ratio (Mw/Mn)of 1.5.

The glass transition temperature of the obtained copolymer (B22) wasmeasured in the same manner as described in Example B1. The result ofthe measurement determined the glass transition temperature of thecopolymer (B22) to be 107.2° C.

Example B23 Preparation of a Combination of the Formula (A14) PlusStyrene in a Molar Ratio of 5.0:95.0

8.63 g of the styrene derivative (A14) and 60.09 g of styrene weredispersed in 42 ml of toluene, and heated to 110° C. in an atmospherewith nitrogen gas stream (50 ml/min). Into this solution was dripped amixture liquid consisting of 42 ml of toluene and 4.54 g of tert-butylperoxy isopropyl monocarbonate (PERBUTYL I, a product name of NOFCORPORATION), and this dripping took 20 minutes. A consequent reactionwas further allowed to proceed for 4 hours at 110° C., and was thencooled. Thereafter, the reaction liquid was dripped into 500 ml ofmethanol, and a gelatinous white deposit separated. After removing thesupernatant liquid by decantation, the deposit was dissolved in 300 mlof tetrahydrofuran. This solution was added to 1.5 liters of methanol,whereby a precipitate occurred, and it was filtered aside and was driedfor 14 hours at 80° C. under a reduced pressure, and 43.12 g of acopolymer (B23) was obtained.

The obtained copolymer (B23) was examined by means of ¹H-NMR under thesame conditions as described in Example B1, and there were observed nopeaks that should, respectively, represent the vinyl group of thestyrene and the styrene derivative (A14) represented by the Formula(A14) as a starting materials before the copolymerization reaction,whereas broad aromatic proton(s) and alkyl chain(s) were observed, andfurthermore, a broad hydroxyl group originating from the styrenederivative (A14) and a broad proton at δ(ppm)=4.94 (—CH₂—O—) wereobserved. From the integrated values of the peaks, it was determinedthat the constituent unit obtained from the styrene derivative (A14) wascontained in the obtained copolymer by 4.30%.

The obtained copolymer (B23) was subjected to FT-IR analysis under thesame conditions as described in Example B1, and the followingobservation was made.

v(cm⁻¹)=3163, 3103, 3082, 3059, 3026, 3001, 2922, 2848, 1942, 1869,1801, 1741, 1670, 1622, 1601, 1583, 1493, 1452, 1441, 1375, 1348, 1298,1255, 1223, 1182, 1140, 1097, 1070, 1028, 1016, 978, 962, 951, 906, 839,820, 758, 698, 654, 621, 540, 459.

The obtained copolymer (B23) is composed of Unit L, which is aconstituent unit obtained from the Compound Example b1-23 and iscontained in the Formula (5), and Unit B, which is the constituent unitrepresented by the Formula (9).

A measurement was conducted on the obtained copolymer (B23) for TG-DTAunder the same conditions described in Example B1. The result of themeasurement is shown in FIG. 23. The measurement result indicated thatthe heat generation temperatures were 419° C. and 532° C., and theweight loss temperatures were 326° C., 405° C. and 516° C.

The obtained copolymer (B23) was subjected to GPC measurement under thesame conditions as described in Example B1. It was confirmed from theresult of the molecular weight distribution measurement conducted undersaid conditions on the copolymer (B23) that the copolymer (B23) has anumber average molecular weight (Mn) of 9383, a weight average molecularweight (Mw) of 36313, and a molecular weight distribution ratio (Mw/Mn)of 3.9.

The glass transition temperature of the obtained copolymer (B23) wasmeasured in the same manner as described in Example B1. The result ofthe measurement determined the glass transition temperature of thecopolymer (B23) to be 91.2° C.

Example B24 Preparation of a Combination of the Formula (A15) PlusStyrene in a Molar Ratio of 5.0:95.0

9.91 g of the styrene derivative (A15) and 60.09 g of styrene weredispersed in 42 ml of toluene, and heated to 110° C. in an atmospherewith nitrogen gas stream (50 ml/min). Into this solution was dripped amixture liquid consisting of 42 ml of toluene and 4.54 g of tert-butylperoxy isopropyl monocarbonate (PERBUTYL I, a product name of NOFCORPORATION), and this dripping took 22 minutes. A consequent reactionwas further allowed to proceed for 4 hours at 110° C., and was thencooled. Thereafter, the reaction liquid was dripped into 500 ml ofmethanol, and a gelatinous white deposit separated. After removing thesupernatant liquid by decantation, the deposit was dissolved in 300 mlof tetrahydrofuran. This solution was added to 1.5 liters of methanol,whereby a precipitate occurred, and it was filtered aside and was driedfor 14 hours at 80° C. under a reduced pressure, and 42.8 g of acopolymer (B24) was obtained.

The obtained copolymer (B24) was examined by means of ¹H-NMR under thesame conditions as described in Example B1, and there were observed nopeaks that should, respectively, represent the vinyl group of thestyrene and the styrene derivative (A15) represented by the Formula(A15) as a starting materials before the copolymerization reaction,whereas broad aromatic proton(s) and alkyl chain(s) were observed, andfurthermore, a broad hydroxyl group originating from the styrenederivative (A15) and a broad proton at δ(ppm)=5.01 (—CH₂—O—) wereobserved. From the integrated values of the peaks, it was determinedthat the constituent unit obtained from the styrene derivative (A15) wascontained in the obtained copolymer by 4.27%.

The obtained copolymer (B24) was subjected to FT-IR analysis under thesame conditions as described in Example B1, and the followingobservation was made.

v(cm⁻¹)=3159, 3105, 3092, 3032, 3005, 2931, 2855, 1945, 1871, 1779,1737, 1659, 1627, 1598, 1499, 1449, 1439, 1381, 1301, 1249, 1225, 1180,1138, 1100, 1073, 1030, 1027, 1020, 981, 943, 902, 844, 814, 749, 700,617, 535, 454.

The obtained copolymer (B24) is composed of Unit M, which is aconstituent unit obtained from the Compound Example a1-28 and iscontained in the Formula (5), and Unit B, which is the constituent unitrepresented by the Formula (9).

A measurement was conducted on the obtained copolymer (B24) for TG-DTAunder the same conditions described in Example B1. The measurementresult indicated that the heat generation temperatures were 423° C. and544° C., and the weight loss temperatures were 319° C. and 508° C.

The obtained copolymer (B24) was subjected to GPC measurement under thesame conditions as described in Example B1. It was confirmed from theresult of the molecular weight distribution measurement conducted undersaid conditions on the copolymer (B24) that the copolymer (B24) has anumber average molecular weight (Mn) of 10430, a weight averagemolecular weight (Mw) of 43356, and a molecular weight distributionratio (Mw/Mn) of 4.2.

The glass transition temperature of the obtained copolymer (B24) wasmeasured in the same manner as described in Example B1. The result ofthe measurement determined the glass transition temperature of thecopolymer (B24) to be 89.7° C.

Example B25

The copolymer obtained in Example B7 and the copolymer obtained inExample B24 were mixed together at a weight ratio of 70:30; thus acopolymer of Example B25 was obtained.

The obtained copolymer (B25) is a mixture of a copolymer composed ofUnit D, which is the constituent unit obtained from the Compound Examplea1-1 and is contained in the Formula (5), and Unit B, which is theconstituent unit represented by the Formula (9), and a copolymercomposed of Unit M, which is the constituent unit obtained from theCompound Example a1-28 and is contained in the Formula (5) and Unit B,which is the constituent unit represented by the Formula (9).

Example B26 Preparation of a Combination of the Formula (A1) PlusStyrene in a Molar Ratio of 5.0:95.0

4.63 g of 4-chloromethylstyrene and 60.09 g of styrene were dissolved in36.3 g of toluene, and heated to 110° C. in an atmosphere with nitrogengas stream (50 ml/min). Into this solution was dripped a mixture liquidconsisting of 33.7 g of toluene and 4.27 g of tert-butyl peroxyisopropyl monocarbonate (PERBUTYL I, a product name of NOF CORPORATION),after this mixture had been subjected to sufficient substitution withnitrogen, and this dripping took 20 minutes. A consequent reaction wasfurther allowed to proceed for 4 hours at 110° C., and was then cooled.Thereafter, the reaction liquid was added to 1 liter of methanol, andthe supernatant was decanted. The polymerized product was dissolved in150 ml of tetrahydrofuran, and the solution was added to 1 liter ofmethanol to cause precipitation and the precipitate was filtered aside.The residue was washed four times with 100 ml of methanol, and was driedfor 10 hours at 60° C. under a reduced pressure, and 64.1 g of acopolymerization intermediate was obtained.

The obtained copolymerization intermediate was examined by means of¹H-NMR under the same conditions as described in Example B1, and therewere observed no peaks that should, respectively, represent the vinylgroup of the styrene as a starting material before the copolymerizationreaction and 4-chloromethylstyrene, whereas broad aromatic proton(s) andalkyl chain(s) and benzil proton, δ(ppm)=4.5 (—CH₂—Cl—), originatingfrom the 4-chloromethylstyrene were observed. From the integrated valuesof the peaks, it was determined that the 4-chloromethylstyrene wascontained in the obtained copolymerization intermediate by 4.33%.

The obtained copolymerization intermediate was subjected to FT-IRanalysis under the same conditions as described in Example B1, and thefollowing observation was made.

v(cm⁻¹)=3103, 3082, 3059, 3026, 3001, 2976, 2924, 2848, 1942, 1869,1801, 1741, 1601, 1583, 1506, 1493, 1452, 1423, 1385, 1373, 1363, 1352,1329, 1313, 1263, 1182, 1155, 1105, 1070, 1028, 1003, 980, 964, 943,906, 839, 758, 698, 621, 540.

The obtained copolymerization intermediate had the following constituentunit.

The obtained copolymerization intermediate was subjected to GPCmeasurement under the same conditions as described in Example B1. It wasconfirmed from the result of the measurement that the copolymerizationintermediate has a number average molecular weight (Mn) of 8287, aweight average molecular weight (Mw) of 20482, and a molecular weightdistribution ratio (Mw/Mn) of 2.5.

10.0 g of the copolymerization intermediate was dissolved in 60 ml oftetrahydrofuran, and 4.3 g of sodium hydride was added and dispersed inthis, which was then stirred for one hour at 70° C. Thereafter 3.3 g of2,5-dihydroxy benzoic acid was added and a consequent reaction wasallowed to proceed for 5 hours at 70° C., and this was cooled to theroom temperature; this was gradually added and dispersed in 1 kg of icewater, and after adding chloroform, extraction was conducted. Next, thiswas washed with water and the chloroform layer was removed, and theremnant was dried with magnesium sulfate and the chloroform wasextracted under a reduced pressure. The deposit was dried for 24 hoursat 80° C. and 7.6 g of a copolymer (B26) was obtained.

The obtained copolymer (B26) was examined by means of ¹H-NMR under thesame conditions as described in Example B1, and it was confirmed fromthe integrated values of the peaks that the benzil proton, δ(ppm)=4.5(—CH₂—Cl—), as a starting material before the reaction was contained by0.90%. Also broad hydroxyl group(s) and broad proton(s) in the vicinityof δ(ppm)=4.9 (—CH₂—O—) were observed, and from the integrated values ofthe peaks, it was determined that the dihydroxy benzoic acid unit wascontained in the obtained copolymer by 4.02%.

The obtained copolymer (B26) was subjected to FT-IR analysis under thesame conditions as described in Example B1, and the followingobservation was made.

v(cm⁻¹)=3435, 3060, 3027, 2922, 2848, 1944, 1873, 1800, 1741, 1678,1616, 1601, 1577, 1493, 1455, 1265, 1215, 1155, 1069, 1028, 906, 758,698, 540.

The obtained copolymer (B26) is composed of Unit D, which is theconstituent unit obtained from the Compound Example a1-1 and iscontained in the Formula (5), and Unit B, which is the constituent unitrepresented by the Formula (9), and Unit S, which originates from acopolymerization intermediate.

A measurement was conducted on the obtained copolymer (B26) for TG-DTAunder the same conditions described in Example B1, and it was observedthat the heat generation temperatures were 345° C. and 539° C., and theweight loss temperatures were 317° C., 389° C. and 512° C.

The obtained copolymer (B26) was subjected to GPC measurement under thesame conditions as described in Example B1. It was confirmed from theresult of the measurement that the copolymer (B26) has a number averagemolecular weight (Mn) of 8157, a weight average molecular weight (Mw) of19775, and a molecular weight distribution ratio (Mw/Mn) of 2.4.

The glass transition temperature of the obtained copolymer (B26) wasmeasured in the same manner as described in Example B1. The result ofthe measurement determined the glass transition temperature of thecopolymer (B26) to be 101.6° C.

Comparative Example 1 Synthesis of the Styrene Derivative Represented byFormula (X1)

90.0 g of 2,5-dihydroxy benzoic acid was dissolved in 1200 ml ofmethanol, and 159.0 g of potassium carbonate was added to this and washeated to 50° C. To this reaction liquid was dripped 72.6 g of arylbromide in the course of 90 minutes, and the reaction was allowed toproceed for 12 hours at 60° C. After cooling this reaction liquid, themethanol was distilled off under a reduced pressure, and the remnant waswashed with hexane. After a filtration, the residue was dispersed in 3liters of water of pH 2, and after adding ethyl acetate, it wasextracted. Thereafter, it was washed with water and the resultant ethylacetate was removed, drying was conducted with magnesium sulfate, andthe ethyl acetate was distilled off to obtain a deposit. This depositwas dissolved in methanol and dripped into water, and was reprecipitatedand the deposit was filtered aside. This reprecipitation was repeatedtwice, and the residue was dried for 48 hours at 80° C., and 26.5 g of astyrene derivative represented by the following Formula (X1) wasobtained (yield=23.8%).

Two kinds of polymer (Y1) made from the styrene derivative representedby the Formula (X1) and styrene(Preparation of a Combination of the Formula (X1) Plus Styrene in aMolar Ratio of 5.0:95.0)

4.68 g of styrene derivative (X1) and 60.09 g of styrene were dispersedin 39 ml of toluene, and was heated to 110° C. in an atmosphere withnitrogen gas stream (50 ml/min). Into this solution was dripped amixture liquid consisting of 39 ml of toluene and 4.27 g of tert-butylperoxy isopropyl monocarbonate (PERBUTYL I, a product name of NOFCORPORATION), and this dripping took 25 minutes. A consequent reactionwas further allowed to proceed for 4 hours at 110° C., and was thencooled. Thereafter, the reaction liquid was solved in 150 ml oftetrahydrofuran. This solution was dripped in methanol and a reactionproduct precipitated and the precipitate was filtered aside and driedfor 20 hours at 90° C. under a reduced pressure, and 47.3 g of acopolymer (Y1) was obtained.

The volume resistive value was measured under the same condition asdescribed in Example B1, and it was found that the copolymer (Y1) has avolume resistive value of 3.7×10¹⁴ Ωcm.

The obtained copolymer (Y1) is composed of Unit K, which is aconstituent unit shown below, and Unit B, which is the constituent unitrepresented by the Formula (9).

Comparative Example 2 Synthesis of Styrene Derivative Represented byFormula (X2)

50.0 g of p-cresol was dissolved in 450 ml of acetone, to which 94.5 gof potassium carbonate was added, and this was heated to 56° C. Intothis reaction mixture was dripped 72.7 g of 4-(chloromethyl)styrene inthe course of 30 minutes, and the consequent reaction was allowed toproceed for 12 hours at 56° C. This reaction liquid was cooled andfiltered, and the acetone, which was the filtrate, was distilled offunder a reduced pressure, and the resultant residue was washed withhexane. After the filtration, the residue was recrystallized withtoluene. Then, filtered again, the residue was dried at 80° C. for 48hours, and 43.2 g of a styrene derivative represented by the belowformula (X2) was obtained (yield=42.5%).

Two kinds of polymer (Y2) made from the styrene derivative representedby the Formula (X2) and styrene(Preparation of a Combination of Formula (X2) Plus Styrene in a MolarRatio of 5.0:95.0)

3.56 g of styrene derivative (X2) and 31.44 g of styrene were dispersedin 21 ml of toluene, and was heated to 110° C. in an atmosphere withnitrogen gas stream (50 ml/min). Into this solution was dripped amixture liquid consisting of 21 ml of toluene and 2.31 g of tert-butylperoxy isopropyl monocarbonate (PERBUTYL I, a product name of NOFCORPORATION), and this dripping took 17 minutes. A consequent reactionwas further allowed to proceed for 4 hours at 110° C., and was thencooled, and this was dissolved in 150 ml of tetrahydrofuran. Thissolution was dripped in methanol and a reaction product precipitated andthe precipitate was filtered aside and dried for 20 hours at 90° C.under a reduced pressure, and 27.9 g of a copolymer (Y2) was obtained.

The obtained copolymer (Y2) is composed of Unit N, which is aconstituent unit shown below, and Unit B, which is the constituent unitrepresented by the Formula (9).

Comparative Example 3

A commercially available polyparavinylphenol represented by Formula (Y3)was used, which is the Compound Example No. 1-1 described in JapanesePatent Application Publication No. H06-95435, (manufactured by MaruzenPetrochemical Co., Ltd; product name: Maruka Lyncur M; grade name: H-2;Mw: 19800-24200; Mn: 3600-4400).

Comparative Example 4

A commercially available copolymer compound made from vinyl phenol andmethyl methacrylate represented by Formula (Y4) was used, which is thecompound No. 1-3 described in Japanese Patent Application PublicationNo. H06-95435, (manufactured by Maruzen Petrochemical Co., Ltd; productname. Maruka Lyncur CMM; Mw: 8000-12000; Mn: 3000-5000).

Comparative Example 5

A commercially available copolymer compound made from vinyl phenol andstyrene represented by Formula (Y5) was used, which is the compound No.1-4 described in Japanese Patent Application Publication No. H06-95435,(manufactured by Maruzen Petrochemical Co., Ltd; product name: MarukaLyncur CST; Mw: 3000-5000; Mn: 1900-3300).

Example C1 Estimation of Charge Controllability of Charge Control Agentsby Means of Electrostatic Propensity Test A

First, one weight part of the styrene derivative (A1) obtained in theprevious example and 100 weight parts of styrene-acryl copolymer resin(manufactured by Mitsui Chemicals Co., Ltd.; product name: CPR-100) weremixed together preparatively, and the mixture was melted and kneaded bya heater roller machine (manufactured by Kurimoto Ltd.; product name:S-1, KRC Kneader). After cooling, the dough was roughly pulverized by asuper centrifugal pulverizer (manufactured by Retsch Inc.; product name:ULTRA CENTRIFUGAL MILL, sieve mesh size: 1.5 mm), and using an air jetmill equipped with a classifier (manufactured by SEISHIN ENTERPRISE CO.,LTD.; product name: CO-JET) and a laser diffraction/lightscattering-type grain diameter distribution analyzer (manufactured byHORIBA, LTD.; product name Partica LA-950), the average grain diameterwas measured and then the matter was finely pulverized to have a size of9.5-10.5 micrometers. 2.5 weight parts of this resin grain and 50.0weight parts of iron powder carrier (manufactured by Powdertech Co.,Ltd.; product name TEFV200/300) were poured into a 100-ml ointmentcontainer, and it was turned at a speed of 100 rpm on a ball mill rotarytable (manufactured by ASAHI-RIKA Co., Ltd.; product name: Small-SizeBall Mill Rotary Table AV-1), and at predetermined intervals of time themixture sample was taken, and the electrostatic charge amount wasmeasured under the following conditions by means of a blow-offelectrostatic charge amount analyzer (manufactured by Toshiba ChemicalCorp.; product name: TB-200). The thus obtained results of negativechargeability verification data are shown in Table 27 and FIG. 24.Measurement conditions: metal sieve mesh size was 35 micrometers;pressure was 10.0 kPa; suction force was 10.0 kPa; suction duration was10.0 seconds.

Next, the styrene derivatives A2, A4, A5, A8, A10, A12, A13 and A14,which were obtained in Examples and the comparative compounds X1 and X2were subjected to the same electrostatic propensity test A, to which thestyrene derivative A1 had been subjected. The results are shown in Table27 and FIG. 24.

TABLE 27 Stirring Duration Electrostatic Charge Amount (−μC/g) (min.) A1A2 A4 A5 A8 A10 A12 A13 A14 X1 X2 0 0.00 0.00 0.00 0.00 0.00 0.00 0.000.00 0.00 0.00 0.00 0.5 2.40 5.25 4.20 3.75 0.90 0.53 3.38 4.58 2.930.43 −0.50 0.75 3.60 6.90 5.10 5.40 2.10 1.35 4.58 6.39 4.74 0.52 −1.431 4.95 8.33 6.15 6.83 3.45 2.03 6.30 7.96 6.31 0.72 −1.61 2 7.88 11.039.08 9.53 6.38 4.73 8.78 10.70 9.53 1.39 −0.78 3 9.60 13.13 10.65 12.238.10 6.30 10.80 13.24 12.01 1.84 −0.18 5 11.85 15.83 13.95 14.33 10.358.33 13.28 16.03 14.87 2.55 0.40 10 16.43 19.80 18.38 19.13 14.93 12.5317.33 20.24 19.09 3.73 1.26 20 21.60 22.80 21.83 21.00 20.10 16.05 23.1823.30 21.27 4.71 1.95 30 23.63 24.30 21.98 19.80 22.13 16.50 26.93 24.6021.12 5.54 2.29

Example C2 Environmental Stability Rating of the Charge Control Agentswhich is the Resin Grain Obtained in Example C1

Using the resin grains obtained in Example C1, the styrene derivativesA1, A2, A4, A5, A8, A10, A12, A13 and A14, which had been obtained inExamples, and the comparative compounds X1 and X2 were rated in terms ofenvironmental stability. The results are shown in Table 28.

50.0 weight parts of iron powder carrier (manufactured by PowdertechCo., Ltd.; product name TEFV200/300) plus each one, respectively, of theresin grain species prepared in the same manner as in theafore-mentioned electrostatic propensity test A were poured in a 100-mlointment container, and a lid having a 1-cm hole in the middle wasplaced on it. This was set in a ball mill machine (manufactured byASAHI-RIKA Co., Ltd.; product name: Ball Mill Rotary Table), which wasinstalled inside a thermo-hygrostat (manufactured by Tokyo Rika Mfg.Co., Ltd.; product name: Enviros KCL-2000W), and each was let to sit for24 hours in respective environment of a predetermined temperature and apredetermined humidity. After the 24 hours, while the 100-ml ointmentcontainer was kept rotating at 100 rpm, the respective mixture was takenout after 15-minute stirring, and the electrostatic charge amount wasmeasured under the following conditions by means of a blow-offelectrostatic charge amount analyzer (manufactured by Toshiba ChemicalCorp.; product name: TB-200). Measurement conditions: metal sieve meshsize was 34 micrometers; pressure was 10.0 kPa; suction force was 10.0kPa; suction duration was 10.0 seconds.

TABLE 28 Electrostatic Charge Amount (μC/g) Saturation Low Temperature &High Temperature & Example Charge Low Humidity (LL) High Humidity (HH)Environmental Stability No. Amount 20° C., 30% RH 30° C., 80% RH |LLval.| − |HH val.| |LL val.|/|HH val.| A1 −23.63 −25.92 −11.91 14.01 2.18A2 −24.30 −27.36 −12.26 15.10 2.23 A4 −21.98 −26.19 −11.08 15.11 2.36 A5−21.00 −25.20 −9.95 15.25 2.53 A8 −22.13 −24.12 −11.17 12.95 2.16 A10−16.50 −19.26 −8.32 10.94 2.31 A12 −26.93 −27.81 −13.52 14.29 2.06 A13−24.60 −27.12 −12.70 14.42 2.14 A14 −21.12 −26.70 −12.30 14.40 2.17 X1−2.82 −3.30 −0.61 2.69 5.41 X2 −2.29 −2.98 −0.45 2.53 6.62In Table 28, “LL” stands for low temperature and low humidity, and “HH”stands for high temperature and high humidity.

Example C3 Estimation of Charge Controllability of Charge Control Agentsby Means of Electrostatic Propensity Test B

First, one weight part of the styrene derivative (A1) obtained in theprevious example and 100 weight parts of polyester resin (manufacturedby Mitsubishi Rayon Co., Ltd.; product name: ER-508) were mixed togetherpreparatively, and the mixture was melted and kneaded by a heater rollermachine (manufactured by Kurimoto Ltd.; product name: S-1, KRC Kneader).After cooling, the dough was roughly pulverized by a super centrifugalpulverizer (manufactured by Retsch Inc.; product name: ULTRA CENTRIFUGALMILL, sieve mesh size: 1.5 mm), and using an air jet mill equipped witha classifier (manufactured by SEISHIN ENTERPRISE CO., LTD.; productname: CO-JET) and a laser diffraction/light scattering-type graindiameter distribution analyzer (manufactured by HORIBA, LTD.; productname Partica LA-950), the average grain diameter was measured and thenthe matter was finely pulverized to have a size of 9.5-10.5 micrometers.2.5 weight parts of this resin grain and 50.0 weight parts of ironpowder carrier (manufactured by Powdertech Co., Ltd.; product nameTEFV200/300) were poured into a 100-ml ointment container, and it wasturned at a speed of 100 rpm on a ball mill rotary table (manufacturedby ASAHI-RIKA Co., Ltd.; product name: Small-Size Ball Mill Rotary TableAV-1), and at predetermined intervals of time the mixture sample wastaken, and the electrostatic charge amount was measured under thefollowing conditions by means of a blow-off electrostatic charge amountanalyzer (manufactured by Toshiba Chemical Corp.; product name: TB-200).The thus obtained results of negative chargeability verification dataare shown in Table 29 and FIG. 25.

Measurement Conditions:

metal sieve mesh size was 34 micrometers; pressure was 10.0 kPa;

suction force was 10.0 kPa; suction duration was 10.0 seconds.

The styrene derivatives A2, A4, A5, A8, A10, A12, A13 and A14, which hadbeen obtained in Examples, and the comparative compounds X1 and X2 weresubjected to the same electrostatic propensity test B, to which thestyrene derivative A1 had been subjected. The results are shown in Table29 and FIG. 25.

TABLE 29 Stirring Duration Electrostatic Charge Amount (−μC/g) (min.) A1A2 A4 A5 A8 A10 A12 A13 A14 X1 X2 0 0.00 0.00 0.00 0.00 0.00 0.00 0.000.00 0.00 0.00 0.00 0.5 3.78 7.46 6.76 5.77 2.68 2.10 5.05 8.07 2.582.53 0.29 0.75 5.72 11.70 8.40 8.20 3.94 3.25 7.02 12.96 4.03 3.03 0.181 7.77 14.20 8.73 10.37 5.56 4.78 9.78 15.06 5.89 3.68 0.31 2 10.8118.10 13.91 13.91 9.66 7.56 13.12 18.76 11.59 5.79 0.65 3 13.28 20.1016.27 16.80 11.92 9.40 15.03 21.10 14.00 7.26 1.05 5 16.54 23.60 19.3620.14 15.49 12.28 18.24 24.00 18.57 9.66 1.52 10 22.57 27.60 25.20 26.3820.73 17.79 24.08 27.00 23.82 12.14 2.26 20 29.92 32.38 30.18 29.0727.19 21.68 32.22 31.72 30.44 14.71 2.60 30 32.49 33.79 31.82 29.4030.13 22.31 36.68 33.01 31.36 15.82 2.94

Example C4 Environmental Stability Rating of the Charge Control Agentswhich is the Resin Grain Obtained in Example C3

Using the resin grains obtained in Example C3, the styrene derivativesA1, A2, A4, A5, A8, A10, A12, A13 and A14, which had been obtained inExamples, and the comparative compounds X1 and X2 were rated in terms ofenvironmental stability. The results are shown in Table 30.

50.0 weight parts of iron powder carrier (manufactured by PowdertechCo., Ltd.; product name TEFV200/300) plus each one, respectively, of theresin grain species prepared in the same manner as in theafore-mentioned electrostatic propensity test B were poured in a 100-mlointment container, and a lid having a 1-cm hole in the middle wasplaced on it. This was set in a ball mill machine (manufactured byASAHI-RIKA Co., Ltd.; product name: Ball Mill Rotary Table), which wasinstalled inside a thermo-hygrostat (manufactured by Tokyo Rika Mfg.Co., Ltd.; product name: Enviros KCL-2000W), and each was let to sit for24 hours in respective environment of a predetermined temperature and apredetermined humidity. After the 24 hours, while the 100-ml ointmentcontainer was kept rotating at 100 rpm, the respective mixture was takenout after 15-minute stirring, and the electrostatic charge amount wasmeasured under the following conditions by means of a blow-offelectrostatic charge amount analyzer (manufactured by Toshiba ChemicalCorp.; product name: TB-200). Measurement conditions: metal sieve meshsize was 34 micrometers; pressure was 10.0 kPa; suction force was 10.0kPa; suction duration was 10.0 seconds.

TABLE 30 Electrostatic Charge Amount (μC/g) Saturation Low Temperature &High Temperature & Example Charge Low Humidity (LL) High Humidity (HH)Environmental Stability No. Amount 20° C., 30% RH 30° C., 80% RH |LLval.| − |HH val.| |LL val.|/|HH val.| A1 −32.49 −39.10 −12.19 26.91 3.21A2 −33.79 −42.29 −15.96 26.33 2.65 A4 −31.82 −39.43 −12.30 27.14 3.21 A5−29.40 −37.99 −13.15 24.84 2.89 A8 −30.13 −35.55 −12.04 23.51 2.95 A10−22.31 −28.38 −8.51 28.02 2.99 A12 −36.68 −42.09 −14.06 19.88 3.34 A13−33.01 −43.56 −18.69 24.87 2.33 A14 −31.36 −36.35 −14.43 21.92 2.52 X1−15.82 −15.60 −2.69 12.91 5.80 X2 −2.94 −3.81 −0.36 3.45 10.58

Example C5 Estimation of Charge Controllability of Charge Control Resinsby Means of Electrostatic Propensity Test A

From charge control resins, which had been obtained in Examples, such as(styrene-based resins) B1, B4, B5, B7, B9, B10, B11, B12, B14, B15, B21,B22, B23, B25 and the comparative resins such as Y1, Y2, Y3, Y4 and Y5,resin grains were obtained in the same manner as in Example C1, andtheir charge controllability was rated. The thus obtained results ofnegative chargeability verification data are shown in Table 31, Table32, Table 33, FIG. 26, FIG. 27 and FIG. 28.

TABLE 31 Stirring Duration Electrostatic Charge Amount (−μC/g) (min.) B1B4 B5 B7 B9 B10 B11 B12 0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.52.19 0.41 4.47 1.00 1.68 1.24 1.88 1.43 0.75 3.27 0.60 5.82 1.65 2.782.11 2.62 2.28 1 4.17 1.04 6.66 2.15 3.71 2.66 3.16 3.01 2 6.29 1.688.77 3.75 6.33 4.19 4.88 4.34 3 8.18 2.22 10.80 5.89 7.48 5.07 6.21 5.535 11.20 3.20 12.84 7.58 9.77 6.43 7.91 6.83 10 14.40 4.58 15.54 10.0013.13 8.73 10.20 9.90 20 16.23 6.40 16.92 12.36 15.92 11.36 12.09 11.7530 16.40 6.93 17.47 13.27 16.89 12.56 12.89 12.23

TABLE 32 Stirring Duration Electrostatic Charge Amount (−μC/g) (min.)B14 B15 B21 Y1 Y2 Y3 Y4 Y5 0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.50.50 1.73 0.66 0.62 0.61 0.06 0.08 0.12 0.75 0.61 2.88 1.24 0.72 0.770.12 0.11 0.22 1 0.74 3.23 1.51 0.78 1.14 0.46 0.44 0.40 2 1.44 4.802.21 1.04 1.38 0.62 0.56 0.66 3 2.00 6.06 2.92 1.43 1.84 0.82 0.79 0.705 2.80 7.96 4.00 1.51 2.35 1.05 0.99 1.20 10 3.49 11.35 6.16 1.90 2.961.28 1.13 1.35 20 4.20 14.40 8.76 2.00 3.52 1.41 1.23 1.44 30 4.40 15.3210.58 2.07 3.46 1.49 1.40 1.56

TABLE 33 Stirring Duration Electrostatic Charge Amount (−μC/g) (min.)B22 B23 B25 Y1 Y2 Y3 Y4 Y5 0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.51.92 0.94 1.64 0.62 0.61 0.06 0.08 0.12 0.75 2.89 1.81 2.45 0.72 0.770.12 0.11 0.22 1 3.70 2.36 3.52 0.78 1.14 0.46 0.44 0.40 2 6.04 3.895.43 1.04 1.38 0.62 0.56 0.66 3 7.83 4.77 6.85 1.43 1.84 0.82 0.79 0.705 10.47 5.80 9.39 1.51 2.35 1.05 0.99 1.20 10 13.73 6.98 11.75 1.90 2.961.28 1.13 1.35 20 15.42 9.10 12.80 2.00 3.52 1.41 1.23 1.44 30 15.8010.94 12.30 2.07 3.46 1.49 1.40 1.56

Example C6 Environmental Stability Rating of the Resin Grains Obtainedin Example C5

Using the resin grains of Example C5, the charge control resins, whichhad been obtained in Examples, such as (styrene-based resins) B1, B4,B5, B7, B9, B10, B11, B12, B14, B15, B21, B22, B23, B25 and thecomparative resins such as Y1, Y2, Y3, Y4 and Y5, were rated in terms ofenvironmental stability in the same manner as in Example C2. The resultsare shown in Table 34.

TABLE 34 Electrostatic Charge Amount (μC/g) Saturation Low Temperature &High Temperature & Example Charge Low Humidity (LL) High Humidity (HH)Environmental Stability No. Amount 20° C., 30% RH 30° C., 80% RH |LLval.| − |HH val.| |LL val.|/|HH val.| B1 −16.40 −19.77 −14.38 5.39 1.38B4 −6.93 −8.28 −5.60 2.68 1.48 B5 −17.47 −20.50 −14.01 6.50 1.46 B7−13.27 −14.83 −10.68 4.16 1.39 B9 −16.89 −19.70 −13.58 6.12 1.45 B10−12.56 −14.23 −10.14 4.09 1.40 B11 −12.89 −15.31 −10.39 4.92 1.47 B12−12.23 −14.80 −9.84 4.96 1.50 B14 −4.40 −5.35 −3.55 1.80 1.51 B15 −15.32−18.05 −12.97 5.09 1.39 B21 −10.58 −11.81 −7.46 4.35 1.58 B22 −15.80−20.00 −14.22 5.78 1.41 B23 −10.94 −12.22 −7.85 4.37 1.56 B25 −12.30−21.60 −13.90 7.70 1.55 Y1 −2.07 −3.70 −0.66 3.04 5.64 Y2 −3.46 −5.52−1.77 3.76 3.12 Y3 −1.49 −2.49 −0.19 2.30 12.98 Y4 −1.40 −2.78 −0.222.56 12.62 Y5 −1.56 −1.73 −0.25 1.48 6.97

Example C7 Estimation of Charge Controllability of Charge Control Resinsby Means of Electrostatic Propensity Test B

From charge control resins, which had been obtained in Examples, such as(styrene-based resins) B1, B4, B5, B7, B9, B10, B11, B12, B14, B15, B21,B22, B23, B25 and the comparative resins such as Y1, Y2, Y3, Y4 and Y5,resin grains were obtained in the same manner as in Example C3, andtheir charge controllability was rated. The thus obtained results ofnegative chargeability verification data are shown in Table 35, Table36, Table 37, FIG. 29, FIG. 30 and FIG. 31.

TABLE 35 Stirring Duration Electrostatic Charge Amount (−μC/g) (min.) B1B4 B5 B7 B9 B10 B11 B12 0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.53.08 0.91 5.03 1.30 2.50 1.61 2.60 2.07 0.75 4.51 1.33 6.62 2.15 3.802.74 3.58 3.21 1 5.88 1.67 8.34 2.96 6.20 3.46 4.43 4.45 2 9.54 3.0211.24 5.93 9.94 5.45 6.34 6.65 3 11.66 3.72 13.52 8.20 12.18 7.27 8.448.32 5 14.00 4.65 16.97 10.97 14.42 9.27 10.28 9.93 10 17.76 6.16 19.7913.64 18.61 11.94 13.15 13.38 20 20.42 8.03 21.38 16.97 21.06 14.6116.18 16.00 30 21.27 9.65 21.66 18.41 21.96 16.85 17.52 17.10

TABLE 36 Stirring Duration Electrostatic Charge Amount (−μC/g) (min.)B14 B15 B21 Y1 Y2 Y3 Y4 Y5 0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.51.02 2.50 0.86 0.81 1.16 0.06 0.25 0.29 0.75 1.36 4.66 1.38 1.37 1.390.12 0.43 0.43 1 1.66 6.03 2.48 1.59 1.62 0.46 0.61 0.72 2 2.52 7.903.45 2.25 2.03 1.01 1.12 0.97 3 3.18 9.75 4.48 2.86 2.42 1.22 1.26 1.125 3.84 11.91 6.28 3.38 3.17 1.40 1.55 1.62 10 5.05 16.43 8.97 4.19 4.031.94 2.30 2.19 20 6.21 19.70 11.93 4.95 4.55 2.19 2.00 2.45 30 6.8220.60 14.90 5.30 4.84 1.94 2.27 2.70

TABLE 37 Stirring Duration Electrostatic Charge Amount (−μC/g) (min.)B22 B23 B25 Y1 Y2 Y3 Y4 Y5 0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.52.74 1.29 1.13 0.81 1.16 0.06 0.25 0.29 0.75 4.01 2.19 1.92 1.37 1.390.12 0.43 0.43 1 5.23 2.77 2.42 1.59 1.62 0.46 0.61 0.72 2 8.74 4.714.37 2.25 2.03 1.01 1.12 0.97 3 10.80 6.15 5.80 2.86 2.42 1.22 1.26 1.125 13.45 7.76 8.10 3.38 3.17 1.40 1.55 1.62 10 16.78 9.83 10.46 4.19 4.031.94 2.30 2.19 20 19.31 11.38 12.53 4.95 4.55 2.19 2.00 2.45 30 20.2312.76 14.00 5.30 4.84 1.94 2.27 2.70

Example C8 Environmental Stability Rating of the Resin Grains Obtainedin Example C7

Using the resin grains of Example C7, the charge control resins, whichhad been obtained in Examples, such as (styrene-based resins) B1, B4,B5, B7, B9, B10, B11, B12, B14, B15, B21, B22, B23, B25 and thecomparative resins such as Y1, Y2, Y3, Y4 and Y5, were rated in terms ofenvironmental stability in the same manner as in Example C4. The resultsare shown in Table 38.

TABLE 38 Electrostatic Charge Amount (μC/g) Saturation Low Temperature &High Temperature & Example Charge Low Humidity (LL) High Humidity (HH)Environmental Stability No. Amount 20° C., 30% RH 30° C., 80% RH |LLval.| − |HH val.| |LL val.|/|HH val.| B1 −21.27 −23.52 −17.34 6.19 1.36B4 −9.65 −11.58 −6.77 4.81 1.71 B5 −21.66 −24.79 −18.20 6.59 1.36 B7−18.41 −21.79 −14.18 7.62 1.54 B9 −21.96 −24.35 −17.63 6.72 1.38 B10−16.85 −19.12 −12.69 6.43 1.51 B11 −17.52 −20.34 −13.93 6.41 1.46 B12−17.10 −19.87 −13.45 6.42 1.48 B14 −6.82 −7.98 −4.97 3.02 1.61 B15−20.60 −23.60 −16.72 6.88 1.41 B21 −14.90 −17.38 −10.34 7.04 1.68 B22−20.23 −23.78 −16.98 6.79 1.40 B23 −12.76 −15.31 −11.01 4.30 1.39 B25−14.00 −16.30 −12.00 4.30 1.36 Y1 −5.30 −6.36 −2.12 4.24 3.00 Y2 −4.84−8.70 −1.54 7.16 5.65 Y3 −1.94 −3.40 −0.21 3.19 16.19 Y4 −2.27 −3.71−0.09 3.62 41.22 Y5 −2.70 −4.02 −0.15 3.87 26.80

As is clear from the figures, the charge control agent of the presentinvention, which is a charge control resin containing styrene derivativeand copolymer as active ingredients facilitates prompt charge risen upand high charge amount irrespective of high speed rotation or low speedrotation.

INDUSTRIAL APPLICABILITY

The charge control resin of the present invention has, as the polymer tomake its active ingredient, a styrene-based resin which is composed of aconstituent unit having a suitable charge controllability so that theresin can be used as charge imparting agent, charge control agent andenhancer. Also, being excellent in heat resistance, electrostaticpropensity and environmental stability, the resin is useful inindustries wherein various electric charge and electrostatic charge areutilized, for example in commodities such as electrostatic powderypaint, electrophotography toner, electrostatic inkjet recorder,electronic paper, pressure sensitive copying paper and developing agent.The styrene derivative which is used as the charge control monomer tomake this constituent unit of the styrene-based resin can be used as thecharge control agent. According to the method of making the chargecontrol resin of the present invention, it is possible to prepare thecharge control resin which makes the charge control active ingredientfor charge imparting agent, charge control agent and enhancer.

What is claimed is:
 1. A charge control agent, comprising: a chargecontrol resin as an active ingredient, obtained by a process comprisingpolymerizing from 0.01 to 9.5 mol % of a styrene derivative with a vinylgroup-containing monomer in the presence of a polymerization initiator,which is a co-polymerization product of the styrene derivative and thevinyl group-containing monomer, wherein the styrene derivative hasformula (3):

wherein, in formula (3): each R¹ is independently a hydrogen atom, ahydroxyl group, a halogen atom, a carboxy-containing group, astraight-chained alkyl group having 1-18 carbon atoms, a branched alkylgroup having 1-18 carbon atoms, a straight-chained alkoxy group having1-18 carbon atoms, or a branched alkoxy group having 1-18 carbon atoms;R² is a hydrogen atom, a hydroxyl group, a halogen atom, acarboxy-containing group, a straight-chained alkyl group having 1-18carbon atoms, a branched alkyl group having 1-18 carbon atoms, astraight-chained alkoxy group having 1-18 carbon atoms, or a branchedalkoxy group having 1-18 carbon atoms; g is a number of 1-3; h is anumber of 1-3; and M is a hydrogen atom, an alkali metal, astraight-chained alkyl group having 1-18 carbon atoms, a branched alkylgroup having 1-18 carbon atoms, an ammonium radical, or a mixturethereof.
 2. The charge control agent of claim 1, wherein the vinylgroup-containing monomer has formula (4):

wherein, in formula (4): R³, R⁴, and R⁵ are each independently ahydrogen atom, a straight-chained alkyl group having 1-8 carbon atoms, abranched alkyl group having 1-8 carbon atoms, a straight-chained alkoxygroup having 1-8 carbon atoms, a branched alkoxy group having 1-8 carbonatoms, or a halogen atom.
 3. The charge control agent of claim 1,wherein the vinyl group-containing monomer has formula (10):

wherein, in formula (10): R⁶ is a methyl group or a hydrogen atom; andR⁷ is a hydroxyl group or an optionally substituted alkoxy group.
 4. Thecharge control agent of claim 1, wherein the vinyl group-containingmonomer is a hydrophilic unsaturated monomer.
 5. The charge controlagent of claim 4, wherein the hydrophilic unsaturated monomer is anacrylic acid or methacrylic acid.
 6. The charge control agent of claim4, wherein the hydrophilic unsaturated monomer is an acrylic acid alkylester or a methacrylic acid alkyl ester.
 7. The charge control agent ofclaim 6, wherein the acrylic acid alkyl ester is at least one selectedfrom the group consisting of hydroxyethyl acrylate, hydroxypropylacrylate, and 2-hydroxypropyl acrylate, and wherein the methacrylic acidalkyl ester is at least one selected from the group consisting ofhydroxyethyl methacrylate, hydroxypropyl methacrylate, and2-hydroxypropyl methacrylate.
 8. The charge control agent of claim 4,wherein the hydrophilic unsaturated monomer is an acrylamide or amethacrylamide.
 9. The charge control agent of claim 8, wherein theacrylamide is at least one selected from the group consisting ofacrylamide, N-methylol acrylamide, diacetone acrylamide, N-isopropylacrylamide, N,N-diethyl acrylamide, N,N-dimethylaminopropyl acrylamide,and N,N-dimethyl acrylamide, and wherein the methacrylamide is at leastone selected from the group consisting of methacrylamide, N-methylolmethacrylamide, diacetone methacrylamide, N-isopropyl methacrylamide,N,N-diethyl methacrylamide, N,N-dimethylaminopropyl methacrylamide, andN,N-dimethyl methacrylamide.
 10. The charge control agent of claim 4,wherein the hydrophilic unsaturated monomer is an alkylacrylamidesulfonate or a free acid thereof or an ester thereof, or analkylmethacrylamide sulfonate or a free acid thereof or an esterthereof.
 11. The charge control agent of claim 10, wherein thealkylacrylamide sulfonate or the free acid thereof or the ester thereofis at least one selected from the group consisting of an ethylacrylamidesulfonic acid, a propylacrylamide sulfonic acid, and atert-butyl-acrylamidesulfonic acid, and wherein the alkylmethacrylamidesulfonate or the free acid thereof or the ester thereof is at least oneselected from the group consisting of an ethylmethacrylamide sulfonicacid, a propylmethacrylamide sulfonic acid, and atert-butyl-methacrylamidesulfonic acid.
 12. The charge control agent ofclaim 11, wherein the alkylacrylamide sulfonate or the free acid thereofor the ester thereof is a tert-butylacrylamidesulfonic acid, and whereinthe alkylmethacrylamide sulfonate or the free acid thereof or the esterthereof is a tert-butylmethacrylamidesulfonic acid.
 13. The chargecontrol agent of claim 4, wherein the hydrophilic unsaturated monomer isa styrene sulfonic acid.
 14. The charge control agent of claim 4,wherein the hydrophilic unsaturated monomer is a metallyl sulfonic acid.15. The charge control agent of claim 4, wherein the hydrophilicunsaturated monomer is acryloyl morpholine.
 16. The charge control agentof claim 4, wherein the hydrophilic unsaturated monomer isacrylonitrile.
 17. The charge control agent of claim 4, wherein thehydrophilic unsaturated monomer is at least one selected from the groupconsisting of monobutyl maleate, isobutyl maleate, itaconic acid, andfumaric acid.